Pesticidal Active Mixtures Comprising Isoxazoline Compounds I

ABSTRACT

The present invention relates to pesticidal mixtures comprising as active compounds
     1) at least one isoaxazoline compound I of the formula (I)   

     
       
         
         
             
             
         
       
         
         wherein R 1 , R 2 , R 3 , R 4 , R 5  and A are defined in the description; 
         and 
         2) at least one active compound II selected from a group A comprising acteylcholine esterase inhibitors, GABA-gated chloride channel antagonists, sodium channel modulators, nicotinic acteylcholine receptor agonists/antagonists, chloride channel activators, juvenile hormone mimics, compounds affecting the oxidative phosphorylation, inhibitors of the chitin biosynthesis, moulting disruptors, inhibitors of the MET, voltage-dependent sodium channel blockers, inhibitors of the lipid synthesis and other compounds as defined in the description, in synergistically effective amounts. 
       
    
     The invention relates further to methods and use of these mixtures for combating insects, arachnids or nematodes in and on plants, and for protecting such plants being infested with pests, especially also for protecting plant propagation material as like seeds.

This application is a divisional of U.S. patent application Ser. No.13/003,037, filed Jan. 7, 2011, which is a National Stage application ofInternational Application No. PCT/EP2009/058517, filed Jul. 6, 2009,which claims the benefit of U.S. Provisional Application No. 61/079,318,filed Jul. 9, 2008, the entire contents of which are hereby incorporatedherein by reference.

The present invention relates to mixtures of active ingredients havingsynergistically enhanced action and to methods comprising applying saidmixtures.

One typical problem arising in the field of pest control lies in theneed to reduce the dosage rates of the active ingredient in order toreduce or avoid unfavorable environmental or toxicological effectswhilst still allowing effective pest control.

Another problem encountered concerns the need to have available pestcontrol agents which are effective against a broad spectrum of pests.

There also exists the need for pest control agents that combineknow-down activity with prolonged control, that is, fast action withlong lasting action.

Another difficulty in relation to the use of pesticides is that therepeated and exclusive application of an individual pesticidal compoundleads in many cases to a rapid selection of pests which have developednatural or adapted resistance against the active compound in question.Therefore there is a need for pest control agents that help prevent orovercome resistance.

It was therefore an object of the present invention to providepesticidal mixtures which solves at least one of the discussed problemsas reducing the dosage rate, enhancing the spectrum of activity orcombining know-down activity with prolonged control or as to resistancemanagement.

We have found that this object is in part or in whole achieved by thecombination of active compounds defined below.

The present invention relates to pesticidal mixtures comprising asactive compounds

-   1) at least one isoxazoline compound I of formula I:

-   -   wherein    -   A is selected from

-   -   -   and wherein # denotes the bond in formula I;

    -   R¹, R³ are independently from one another selected from        hydrogen, chloro or CF₃;

    -   R² is hydrogen or chloro;

    -   R⁴ is hydrogen or CH₃,

    -   R⁵ is hydrogen, or

    -   R⁴ and R⁵ are together a bridging 1,3-butadienyl group, which        form—together with the aromatic phenylring C they are attached        to—a naphtyl ring;

-   or the tautomers, enantiomers, diastereomers or salts thereof,

-   and

-   2) at least one active compound II selected from group A consisting    of

-   A.1 Acetylcholine esterase inhibitors selected from triazemate or    from the class of carbamates consisting of aldicarb, alanycarb,    benfuracarb, carbaryl, carbofuran, carbosulfan, methiocarb,    methomyl, oxamyl, primicarb, propoxur and thiodicarb or from the    class of organophosphates consisting of acephate, azinphos-ethyl,    azinphos-methyl, chlorfenvinphos, chlorpyrifos, chlorpyrifos-methyl,    demeton-S-methyl, diazinon, dichlorvos/DDVP, dicrotophos,    dimethoate, disulfoton, ethion, fenitrothion, fenthion, isoxathion,    malathion, methamidaphos, methidathion, mevinphos, monocrotophos,    oxymethoate, oxydemeton-methyl, parathion, parathion-methyl,    phenthoate, phorate, phosalone, phosmet, phosphamidon,    pirimiphos-methyl, quinalphos, terbufos, tetrachlorvinphos,    triazophos and trichlorfon;

-   A.2 GABA-gated chloride channel antagonists selected from the    cyclodiene organochlorine endosulfan, from    N-Ethyl-2,2-dimethylpropionamide-2-(2,6-dichloro-α.α.α-trifluoro-p-tolyl)    hydrazon or    N-Ethyl-2,2-dichloro-1-methylcyclopropane-carboxamide-2-(2,6-dichloro-α.α.α-trifluoro-p-tolyl)    hydrazon or from the class of phenylpyrazoles consisting of    acetoprole, ethiprole, fipronil, pyrafluprole, pyriprole,    vaniliprole and the phenylpyrazole compound II.A21:

-   A.3 Sodium channel modulators selected from the class of pyrethroids    consisiting of allethrin, bifenthrin, beta-cyfluthrin, cyfluthrin,    lambda-cyhalothrin, cypermethrin, alpha-cypermethrin,    beta-cypermethrin, zeta-cypermethrin, deltamethrin, esfenvalerate,    etofenprox, fenpropathrin, fenvalerate, flucythrinate, metofluthrin,    permethrin, profluthrin, pyrethrin (pyrethrum), tau-fluvalinate,    silafluofen and tralomethrin;-   A.4 Nicotinic acteylcholine receptor agonists/antagonists selected    from nicotin, cartap hydrochloride or thiocyclam or selected from    the class of neonicotinoids consisting of acteamiprid,    chlothianidin, dinotefuran, imidacloprid, nitenpyram, spinosad    (allosteric agonist), spinetroam (allosteric agonist), thiacloprid,    thiamethoxam and AKD-1022;-   A.5 Chloride channel activators selected from abamectin, emamectin    benzoate, lepimectin or milbemectin;-   A.6 Juvenile hormone mimics selected from hydroprene, kinoprene,    fenoxycarb or pyriproxyfen;-   A.7 Compounds affecting the oxidative phosphorylation selected from    diafenthiuron, fenbutatin oxide, propargite or chlorfenapyr;-   A.8 Inhibitors of the chitin biosynthesis selected from buprofezin    or from the class of benzylureas consisting of bistrifluron,    diflubenzuron, flufenoxuron, hexaflumuron, lufenuron, novaluron or    teflubenzuron;-   A.9 Moulting disruptors selected from cyromazine or from the class    of ecdysone agonists consisting of methoxyfenozide, tebufenozide and    azadirachtin;-   A.10 Mitochondrial electron transport inhibitors selected from    pyridaben, tolfenpyrad or flufenerim.-   A.11 Voltage-dependent sodium channel blockers selected from    indoxacarb or metaflumizone.-   A.12 Inhibitors of the lipid synthesis selected from spirodiclofen,    spiromesifen or spirotetramat.-   A.13 A group of various compounds consisting of amidoflumet,    amitraz, bifenazate, clofentezine, cyenopyrafen, cyflumetofen,    etoxazole, flonicamid, flubendiamine, flupyrazophos, hexythiazox,    piperonyl butoxide, pymetrozine, pyridalyl, pyrifluquinazon,    chlorantraniliprole and the anthranilamid compound II.A^(13.1):

-   and the anthranilamid compounds-   5-Bromo-2-(3-chloro-pyridin-2-yl)-2H-pyrazole-3-carboxylic acid    [4-cyano-2-(1-cyclopropyl-ethylcarbamoyl)-6-methyl-phenyl]-amide,-   5-Bromo-2-(3-chloro-pyridin-2-yl)-2H-pyrazole-3-carboxylic acid    [2-chloro-4-cyano-6-(1-cyclopropyl-ethylcarbamoyl)-phenyl]-amide,-   5-Bromo-2-(3-chloro-pyridin-2-yl)-2H-pyrazole-3-carboxylic acid    [2-bromo-4-cyano-6-(1-cyclopropyl-ethylcarbamoyl)-phenyl]-amide,-   5-Bromo-2-(3-chloro-pyridin-2-yl)-2H-pyrazole-3-carboxylic acid    [2-bromo-4-chloro-6-(1-cyclopropyl-ethylcarbamoyl)-phenyl]-amide,-   5-Bromo-2-(3-chloro-pyridin-2-yl)-2H-pyrazole-3-carboxylic acid    [2,4-dichloro-6-(1-cyclopropyl-ethylcarbamoyl)-phenyl]-amide,-   5-Bromo-2-(3-chloro-pyridin-2-yl)-2H-pyrazole-3-carboxylic acid    [4-chloro-2-(1-cyclopropyl-ethylcarbamoyl)-6-methyl-phenyl]-amide,-   N′-(2-{[5-Bromo-2-(3-chloro-pyridin-2-yl)-2H-pyrazole-3-carbonyl]-amino}-5-chloro-3-methyl-benzoyl)-hydrazinecarboxylic    acid methyl ester,-   N′-(2-{[5-Bromo-2-(3-chloro-pyridin-2-yl)-2H-pyrazole-3-carbonyl]-amino}-5-chloro-3-methyl-benzoyl)-N′-methyl-hydrazinecarboxylic    acid methyl ester,-   N′-(2-{[5-Bromo-2-(3-chloro-pyridin-2-yl)-2H-pyrazole-3-carbonyl]-amino}-5-chloro-3-methyl-benzoyl)-N,N′-dimethyl-hydrazinecarboxylic    acid methyl ester,-   N′-(3,5-Dibromo-2-{[5-bromo-2-(3-chloro-pyridin-2-yl)-2H-pyrazole-3-carbonyl]-amino}-benzoyl)-hydrazinecarboxylic    acid methyl ester,-   N′-(3,5-Dibromo-2-{[5-bromo-2-(3-chloro-pyridin-2-yl)-2H-pyrazole-3-carbonyl]-amino}-benzoyl)-N′-methyl-hydrazinecarboxylic    acid methyl ester and-   N′-(3,5-Dibromo-2-{[5-bromo-2-(3-chloro-pyridin-2-yl)-2H-pyrazole-3-carbonyl]-amino}-benzoyl)-N,N′-dimethyl-hydrazinecarboxylic    acid methyl ester, the aminofuranone compounds-   4-{[(6-Bromopyrid-3-yl)methyl](2-fluoroethyl)amino}furan-2(5H)-on,-   4-{[(6-Fluoropyrid-3-yl)methyl](2,2-difluoroethyl)amino}furan-2(5H)-on,-   4-{[(2-Chloro1,3-thiazolo-5-yl)methyl](2-fluoroethyl)amino}furan-2(5H)-on,-   4-{[(6-Chloropyrid-3-yl)methyl](2-fluoroethyl)amino}furan-2(5H)-on,-   4-{[(6-Chloropyrid-3-yl)methyl](2,2-difluoroethyl)amino}furan-2(5H)-on,-   4-{[(6-Chloro-5-fluoropyrid-3-yl)methyl](methyl)amino}furan-2(5H)-on,-   4-{[(5,6-Dichloropyrid-3-yl)methyl](2-fluoroethyl)amino}furan-2(5H)-on,-   4-{[(6-Chloro-5-fluoropyrid-3-yl)methyl](cyclopropyl)amino}furan-2(5H)-on,-   4-{[(6-Chloropyrid-3-yl)methyl](cyclopropyl)amino}furan-2(5H)-on and-   4-{[(6-Chloropyrid-3-yl)methyl](methyl)amino}furan-2(5H)-on, the    malononitrile compounds    2-(2,2,3,3,4,4,5,5-octafluoropentyl)-2-(3,3,3-trifluoropropyl)malononitrile    (CF₂H—CF₂—CF₂—CF₂—CH₂—C(CN)₂—CH₂—CH₂—CF₃) and    2-(2,2,3,3,4,4,5,5-octafluoropentyl)-2-(3,3,4,4,4-pentafluorobutyl)-malonodinitrile    (CF₂H—CF₂—CF₂—CF₂—CH₂—C(CN)₂—CH₂—CH₂—CF₂—CF₃), the alkynylether    compound    4-But-2-ynyloxy-6-(3,5-dimethyl-piperidin-1-yl)-2-fluoro-pyrimidine,    the sulfoximine compounds II.A^(13.2)

-   and II.A^(13.4)

-   the phtalamid compound (R)-,    (S)-3-Chlor-N1-{2-methyl-4-[1,2,2,2-tetrafluor-1-(trifluormethyl)ethyl]phenyl}-N2-(1-methyl-2-methylsulfonylethyl)phthalamid    (II.A^(13.5)), the pyripyropene compound Cyclopropaneacetic acid,    1,1′-[(3    S,4R,4aR,6S,6aS,12R,12aS,12bS)-4-[[(2-cyclopropylacetyl)oxy]methyl]-1,3,4,4a,5,6,6a,12,12a,12b-decahydro-12-hydroxy-4,6a,12b-trimethyl-11-oxo-9-(3-pyridinyl)-2H,11H-naphtho[2,1-b]pyrano[3,4-e]pyran-3,6-diyl]ester    (II.A^(13.6)) and the pyridazine compound    8-(2-Cyclopropylmethoxy-4-trifluoromethyl-phenoxy)-3-(6-trifluoromethyl-pyridazin-3-yl)-3-aza-bicyclo[3.2.1]octane    (II.A^(13.7))-   in synergistically effective amounts.

Moreover, we have found that simultaneous, that is joint or separate,application of one ore more active compound I and one or more compoundsII or successive application of one or more active compound I and one ormore active compounds II allows enhanced control of pests compared tothe control rates that are possible with the individual compounds.

The present invention also provides methods for the control of insects,acarids or nematodes comprising contacting the insect, acarid ornematode or their food supply, habitat, breeding grounds or their locuswith a pesticidally effective amount of mixtures of at least one activecompound I with at least one active compound II.

Moreover, the present invention also relates to a method of protectingplants from attack or infestation by insects, acarids or nematodescomprising contacting the plant, or the soil or water in which the plantis growing, with a pesticidally effective amount of a mixture of atleast one active compound I with at least one active compound II.

The invention also provides a method for the protection of seeds fromsoil insects and of the seedlings' roots and shoots from soil and foliarinsects which comprises contacting the seeds before sowing and/or afterpregermination with a pesticidally effective amount of a mixture of atleast one active compound I with at least one active compound II.

The invention also provides seeds comprising a mixture of at least oneactive compound I with at least one active compound II.

The invention also relates to the use of a mixture of at least oneactive compound I with at least one active compound II for combatinginsects, arachnids or nematodes.

The invention also provides the use of a mixture of at least one activecompound I with at least one active compound II for combating parasitesin and on animals.

The invention provides further a method for treating, controlling,preventing or protecting animals against infestation or infection byparasites which comprises orally, topically or parenterallyadministering or applying to the animals a parasiticidally effectiveamount of a mixture of at least one active compound I with at least oneactive compound II.

Another aspect of the present invention is a process for the preparationof a composition for treating, controlling, preventing or protectinganimals against infestation or infection by parasites which comprises aparasiticidally effective amount of a mixture of the active compound Iwith at least one active compound II.

Pesticidal active isoxazoline compounds have been described inWO05/085219, WO2007/075459, WO2008/019760 and WO2008/012027. Furtherisoxazoline compounds comprising annelated bicyclic moieties, as annaphtyl group, are disclosed in WO2007/079162. Preparation methods aredescribed in WO 2007/074789 and WO 2007/094313. In general, pesticidalactive isoaxzoline compounds are also described in JP 2007/016017, JP2007/106756, WO 2005/085216, WO 2007/026965, WO 2007/105814, WO2007/125984 WO 2007/026965, JP 2008-239611, WO 2008108448, WO2009/005015, WO 2009/035004, WO 2008/150393, WO 2008/154528, WO2009/002809, WO 2009/003075, WO 2009/025983, WO 2009/051956, WO2009/022746, WO 2009/049846, WO 2008/126665, US 2008/00262057 and WO2009/024541.

The prior art does not disclose pesticidal mixtures comprising selectiveisoxazoline compounds according to the present invention showingunexpected and synergistic effects in combination with otherpesticidically active compounds.

The commercially available compounds of the group A may be found in ThePesticide Manual, 13^(th) Edition, British Crop Protection Council(2003) among other publications. Thiamides derivatives in analogy offormula II.A^(2.1) and their preparation have been described in WO98/28279. Lepimectin is known from Agro Project, PJB Publications Ltd,November 2004. Methidathion and Paraoxon and their preparation have beendescribed in Farm Chemicals Handbook, Volume 88, Meister PublishingCompany, 2001. Acetoprole and its preparation have been described in WO98/28277. Metaflumizone and its preparation have been described in EP-A1462 456. Flupyrazofos has been described in Pesticide Science 54, 1988,p. 237-243 and in U.S. Pat. No. 4,822,779. Pyrafluprole and itspreparation have been described in JP-A 2002-193709 and in WO 01/00614.Pyriprole and its preparation have been described in WO 98/45274 and inU.S. Pat. No. 6,335,357. Amidoflumet and its preparation have beendescribed in U.S. Pat. No. 6,221,890 and in JP-A 21010907. Flufenerimand its preparation have been described in WO 03/007717 and in WO03/007718. Cyflumetofen and its preparation have been described in WO04/080180. Preparation methods for neonicotionids similar to AKD-1022have been described by Zhang, A. et al. in J. Neurochemistry, 75(3),2000. Anthranilamides like chloranthraniliprole and derivatives inanalogy of formula II.A^(13.1) and their preparation have been describedin WO 01/70671; WO 02/48137; WO 03/24222, WO 03/15518, WO 03/15519, WO04/67528; WO 04/33468 and WO 05/118552. Further anthranilamides havealso been described in WO 2008/72743, WO 200872783 and WO 2007/043677.Malononitrile compounds have been described e.g. in WO 02/089579, WO02/090320, WO 02/090321, WO 04/006677, WO 05/068423, WO 05/068432 and WO05/063694. The alkynylether compound is described e.g. in JP 2006131529.Sulfoximine derivatives of and in analogy of formulae II.A^(13.2),II.A^(13.3) or II.A^(13.4) and their preparations have been described inWO 2006/060029. The phthalamide compound (II.^(A13.5)) is known from WO2007/101540 The aminofuranone compounds have been described eg. in WO2007/115644. The pyripyropene derivative (II.A^(13.6)) has beendescribed in WO 2008/66153 and WO 2008/108491. The pyridazin compound(II.A^(13.2)) has been described in JP 2008/115155.

Preferences Preferred Compounds I of Formula I

With regard to their use in the pesticidal mixtures of the presentinvention, compounds I of formula I are preferred, wherein

-   A is A-1, A-4 or A-6;-   R¹, R³ are independently from one another selected from hydrogen,    chloro or CF₃;-   R² is hydrogen or chloro;-   R⁴ is hydrogen oder CH₃,

R⁵ is hydrogen or

-   R⁴ and R⁵ are together a bridging 1,3-butadienyl group, which    form—together with the aromatic phenylring C they are attached to—a    naphtyl ring;

Especially preferred are compounds I of formula I having the followingmeanings:

-   A is A-1, A-4 or A-6;-   R¹, R², R³ are chloro;-   R⁴ is hydrogen oder CH₃,-   R⁵ is hydrogen or-   R⁴ and R⁵ are together a bridging 1,3-butadienyl group, which    form—together with the aromatic phenylring C they are attached to—a    naphtyl ring;

Especially preferred are compounds I of formula I having the followingmeanings:

-   A is A-1, A-4 or A-6;-   R¹, R³ are chloro;-   R² is hydrogen;-   R⁴ is hydrogen oder CH₃,-   R⁵ is hydrogen or-   R⁴ and R⁵ are together a bridging 1,3-butadienyl group, which    form—together with the aromatic phenylring C they are attached to—a    naphtyl ring;

Further preferred are compounds I of formula I having the followingmeanings:

-   A is A-1, A-4 or A-6;-   R¹, R³ are CF₃;-   R² is hydrogen;-   R⁴ is hydrogen oder CH₃,-   R⁵ is hydrogen or-   R⁴ and R⁵ are together a bridging 1,3-butadienyl group, which    form—together with the aromatic phenylring C they are attached to—a    naphtyl ring;-   or-   A is A-1, A-4 or A-6;-   R¹ is CF₃;-   R², R³ are hydrogen;-   R⁴ is hydrogen oder CH₃,-   R⁵ is hydrogen or-   R⁴ and R⁵ are together a bridging 1,3-butadienyl group, which    form—together with the aromatic phenylring C they are attached to—a    naphtyl ring;

Compound I examples of isoxazoline compounds of formula I are given inthe following table C.I.1:

TABLE C.I.1 Compound I A R¹ R² R³ R⁴ R⁵ C.I-1 A-1 H H H H H C.I-2 A-2 HH H H H C.I-3 A-3 H H H H H C.I-4 A-4 H H H H H C.I-5 A-5 H H H H HC.I-6 A-6 H H H H H C.I-7 A-7 H H H H H C.I-8 A-8 H H H H H C.I-9 A-9 HH H H H C.I-10 A-1 H Cl H H H C.I-11 A-2 H Cl H H H C.I-12 A-3 H Cl H HH C.I-13 A-4 H Cl H H H C.I-14 A-5 H Cl H H H C.I-15 A-6 H Cl H H HC.I-16 A-7 H Cl H H H C.I-17 A-8 H Cl H H H C.I-18 A-9 H Cl H H H C.I-19A-1 Cl H H H H C.I-20 A-2 Cl H H H H C.I-21 A-3 Cl H H H H C.I-22 A-4 ClH H H H C.I-23 A-5 Cl H H H H C.I-24 A-6 Cl H H H H C.I-25 A-7 Cl H H HH C.I-26 A-8 Cl H H H H C.I-27 A-9 Cl H H H H C.I-28 A-1 Cl Cl H H HC.I-29 A-2 Cl Cl H H H C.I-30 A-3 Cl Cl H H H C.I-31 A-4 Cl Cl H H HC.I-32 A-5 Cl Cl H H H C.I-33 A-6 Cl Cl H H H C.I-34 A-7 Cl Cl H H HC.I-35 A-8 Cl Cl H H H C.I-36 A-9 Cl Cl H H H C.I-37 A-1 CF₃ H H H HC.I-38 A-2 CF₃ H H H H C.I-39 A-3 CF₃ H H H H C.I-40 A-4 CF₃ H H H HC.I-41 A-5 CF₃ H H H H C.I-42 A-6 CF₃ H H H H C.I-43 A-7 CF₃ H H H HC.I-44 A-8 CF₃ H H H H C.I-45 A-9 CF₃ H H H H C.I-46 A-1 CF₃ Cl H H HC.I-47 A-2 CF₃ Cl H H H C.I-48 A-3 CF₃ Cl H H H C.I-49 A-4 CF₃ Cl H H HC.I-50 A-5 CF₃ Cl H H H C.I-51 A-6 CF₃ Cl H H H C.I-52 A-7 CF₃ Cl H H HC.I-53 A-8 CF₃ Cl H H H C.I-54 A-9 CF₃ Cl H H H C.I-55 A-1 H H Cl H HC.I-56 A-2 H H Cl H H C.I-57 A-3 H H Cl H H C.I-58 A-4 H H Cl H H C.I-59A-5 H H Cl H H C.I-60 A-6 H H Cl H H C.I-61 A-7 H H Cl H H C.I-62 A-8 HH Cl H H C.I-63 A-9 H H Cl H H C.I-64 A-1 H Cl Cl H H C.I-65 A-2 H Cl ClH H C.I-66 A-3 H Cl Cl H H C.I-67 A-4 H Cl Cl H H C.I-68 A-5 H Cl Cl H HC.I-69 A-6 H Cl Cl H H C.I-70 A-7 H Cl Cl H H C.I-71 A-8 H Cl Cl H HC.I-72 A-9 H Cl Cl H H C.I-73 A-1 Cl H Cl H H C.I-74 A-2 Cl H Cl H HC.I-75 A-3 Cl H Cl H H C.I-76 A-4 Cl H Cl H H C.I-77 A-5 Cl H Cl H HC.I-78 A-6 Cl H Cl H H C.I-79 A-7 Cl H Cl H H C.I-80 A-8 Cl H Cl H HC.I-81 A-9 Cl H Cl H H C.I-82 A-1 Cl Cl Cl H H C.I-83 A-2 Cl Cl Cl H HC.I-84 A-3 Cl Cl Cl H H C.I-85 A-4 Cl Cl Cl H H C.I-86 A-5 Cl Cl Cl H HC.I-87 A-6 Cl Cl Cl H H C.I-88 A-7 Cl Cl Cl H H C.I-89 A-8 Cl Cl Cl H HC.I-90 A-9 Cl Cl Cl H H C.I-91 A-1 CF₃ H Cl H H C.I-92 A-2 CF₃ H Cl H HC.I-93 A-3 CF₃ H Cl H H C.I-94 A-4 CF₃ H Cl H H C.I-95 A-5 CF₃ H Cl H HC.I-96 A-6 CF₃ H Cl H H C.I-97 A-7 CF₃ H Cl H H C.I-98 A-8 CF₃ H Cl H HC.I-99 A-9 CF₃ H Cl H H C.I-100 A-1 CF₃ Cl Cl H H C.I-101 A-2 CF₃ Cl ClH H C.I-102 A-3 CF₃ Cl Cl H H C.I-103 A-4 CF₃ Cl Cl H H C.I-104 A-5 CF₃Cl Cl H H C.I-105 A-6 CF₃ Cl Cl H H C.I-106 A-7 CF₃ Cl Cl H H C.I-107A-8 CF₃ Cl Cl H H C.I-108 A-9 CF₃ Cl Cl H H C.I-109 A-1 H H CF₃ H HC.I-110 A-2 H H CF₃ H H C.I-111 A-3 H H CF₃ H H C.I-112 A-4 H H CF₃ H HC.I-113 A-5 H H CF₃ H H C.I-114 A-6 H H CF₃ H H C.I-115 A-7 H H CF₃ H HC.I-116 A-8 H H CF₃ H H C.I-117 A-9 H H CF₃ H H C.I-118 A-1 H Cl CF₃ H HC.I-119 A-2 H Cl CF₃ H H C.I-120 A-3 H Cl CF₃ H H C.I-121 A-4 H Cl CF₃ HH C.I-122 A-5 H Cl CF₃ H H C.I-123 A-6 H Cl CF₃ H H C.I-124 A-7 H Cl CF₃H H C.I-125 A-8 H Cl CF₃ H H C.I-126 A-9 H Cl CF₃ H H C.I-127 A-1 Cl HCF₃ H H C.I-128 A-2 Cl H CF₃ H H C.I-129 A-3 Cl H CF₃ H H C.I-130 A-4 ClH CF₃ H H C.I-131 A-5 Cl H CF₃ H H C.I-132 A-6 Cl H CF₃ H H C.I-133 A-7Cl H CF₃ H H C.I-134 A-8 Cl H CF₃ H H C.I-135 A-9 Cl H CF₃ H H C.I-136A-1 Cl Cl CF₃ H H C.I-137 A-2 Cl Cl CF₃ H H C.I-138 A-3 Cl Cl CF₃ H HC.I-139 A-4 Cl Cl CF₃ H H C.I-140 A-5 Cl Cl CF₃ H H C.I-141 A-6 Cl ClCF₃ H H C.I-142 A-7 Cl Cl CF₃ H H C.I-143 A-8 Cl Cl CF₃ H H C.I-144 A-9Cl Cl CF₃ H H C.I-145 A-1 CF₃ H CF₃ H H C.I-146 A-2 CF₃ H CF₃ H HC.I-147 A-3 CF₃ H CF₃ H H C.I-148 A-4 CF₃ H CF₃ H H C.I-149 A-5 CF₃ HCF₃ H H C.I-150 A-6 CF₃ H CF₃ H H C.I-151 A-7 CF₃ H CF₃ H H C.I-152 A-8CF₃ H CF₃ H H C.I-153 A-9 CF₃ H CF₃ H H C.I-154 A-1 CF₃ Cl CF₃ H HC.I-155 A-2 CF₃ Cl CF₃ H H C.I-156 A-3 CF₃ Cl CF₃ H H C.I-157 A-4 CF₃ ClCF₃ H H C.I-158 A-5 CF₃ Cl CF₃ H H C.I-159 A-6 CF₃ Cl CF₃ H H C.I-160A-7 CF₃ Cl CF₃ H H C.I-161 A-8 CF₃ Cl CF₃ H H C.I-162 A-9 CF₃ Cl CF₃ H HC.I-163 A-1 H H H CH₃ H C.I-164 A-2 H H H CH₃ H C.I-165 A-3 H H H CH₃ HC.I-166 A-4 H H H CH₃ H C.I-167 A-5 H H H CH₃ H C.I-168 A-6 H H H CH₃ HC.I-169 A-7 H H H CH₃ H C.I-170 A-8 H H H CH₃ H C.I-171 A-9 H H H CH₃ HC.I-172 A-1 H Cl H CH₃ H C.I-173 A-2 H Cl H CH₃ H C.I-174 A-3 H Cl H CH₃H C.I-175 A-4 H Cl H CH₃ H C.I-176 A-5 H Cl H CH₃ H C.I-177 A-6 H Cl HCH₃ H C.I-178 A-7 H Cl H CH₃ H C.I-179 A-8 H Cl H CH₃ H C.I-180 A-9 H ClH CH₃ H C.I-181 A-1 Cl H H CH₃ H C.I-182 A-2 Cl H H CH₃ H C.I-183 A-3 ClH H CH₃ H C.I-184 A-4 Cl H H CH₃ H C.I-185 A-5 Cl H H CH₃ H C.I-186 A-6Cl H H CH₃ H C.I-187 A-7 Cl H H CH₃ H C.I-188 A-8 Cl H H CH₃ H C.I-189A-9 Cl H H CH₃ H C.I-190 A-1 Cl Cl H CH₃ H C.I-191 A-2 Cl Cl H CH₃ HC.I-192 A-3 Cl Cl H CH₃ H C.I-193 A-4 Cl Cl H CH₃ H C.I-194 A-5 Cl Cl HCH₃ H C.I-195 A-6 Cl Cl H CH₃ H C.I-196 A-7 Cl Cl H CH₃ H C.I-197 A-8 ClCl H CH₃ H C.I-198 A-9 Cl Cl H CH₃ H C.I-199 A-1 CF₃ H H CH₃ H C.I-200A-2 CF₃ H H CH₃ H C.I-201 A-3 CF₃ H H CH₃ H C.I-202 A-4 CF₃ H H CH₃ HC.I-203 A-5 CF₃ H H CH₃ H C.I-204 A-6 CF₃ H H CH₃ H C.I-205 A-7 CF₃ H HCH₃ H C.I-206 A-8 CF₃ H H CH₃ H C.I-207 A-9 CF₃ H H CH₃ H C.I-208 A-1CF₃ Cl H CH₃ H C.I-209 A-2 CF₃ Cl H CH₃ H C.I-210 A-3 CF₃ Cl H CH₃ HC.I-211 A-4 CF₃ Cl H CH₃ H C.I-212 A-5 CF₃ Cl H CH₃ H C.I-213 A-6 CF₃ ClH CH₃ H C.I-214 A-7 CF₃ Cl H CH₃ H C.I-215 A-8 CF₃ Cl H CH₃ H C.I-216A-9 CF₃ Cl H CH₃ H C.I-217 A-1 H H Cl CH₃ H C.I-218 A-2 H H Cl CH₃ HC.I-219 A-3 H H Cl CH₃ H C.I-220 A-4 H H Cl CH₃ H C.I-221 A-5 H H Cl CH₃H C.I-222 A-6 H H Cl CH₃ H C.I-223 A-7 H H Cl CH₃ H C.I-224 A-8 H H ClCH₃ H C.I-225 A-9 H H Cl CH₃ H C.I-226 A-1 H Cl Cl CH₃ H C.I-227 A-2 HCl Cl CH₃ H C.I-228 A-3 H Cl Cl CH₃ H C.I-229 A-4 H Cl Cl CH₃ H C.I-230A-5 H Cl Cl CH₃ H C.I-231 A-6 H Cl Cl CH₃ H C.I-232 A-7 H Cl Cl CH₃ HC.I-233 A-8 H Cl Cl CH₃ H C.I-234 A-9 H Cl Cl CH₃ H C.I-235 A-1 Cl H ClCH₃ H C.I-236 A-2 Cl H Cl CH₃ H C.I-237 A-3 Cl H Cl CH₃ H C.I-238 A-4 ClH Cl CH₃ H C.I-239 A-5 Cl H Cl CH₃ H C.I-240 A-6 Cl H Cl CH₃ H C.I-241A-7 Cl H Cl CH₃ H C.I-242 A-8 Cl H Cl CH₃ H C.I-243 A-9 Cl H Cl CH₃ HC.I-244 A-1 Cl Cl Cl CH₃ H C.I-245 A-2 Cl Cl Cl CH₃ H C.I-246 A-3 Cl ClCl CH₃ H C.I-247 A-4 Cl Cl Cl CH₃ H C.I-248 A-5 Cl Cl Cl CH₃ H C.I-249A-6 Cl Cl Cl CH₃ H C.I-250 A-7 Cl Cl Cl CH₃ H C.I-251 A-8 Cl Cl Cl CH₃ HC.I-252 A-9 Cl Cl Cl CH₃ H C.I-253 A-1 CF₃ H Cl CH₃ H C.I-254 A-2 CF₃ HCl CH₃ H C.I-255 A-3 CF₃ H Cl CH₃ H C.I-256 A-4 CF₃ H Cl CH₃ H C.I-257A-5 CF₃ H Cl CH₃ H C.I-258 A-6 CF₃ H Cl CH₃ H C.I-259 A-7 CF₃ H Cl CH₃ HC.I-260 A-8 CF₃ H Cl CH₃ H C.I-261 A-9 CF₃ H Cl CH₃ H C.I-262 A-1 CF₃ ClCl CH₃ H C.I-263 A-2 CF₃ Cl Cl CH₃ H C.I-264 A-3 CF₃ Cl Cl CH₃ H C.I-265A-4 CF₃ Cl Cl CH₃ H C.I-266 A-5 CF₃ Cl Cl CH₃ H C.I-267 A-6 CF₃ Cl ClCH₃ H C.I-268 A-7 CF₃ Cl Cl CH₃ H C.I-269 A-8 CF₃ Cl Cl CH₃ H C.I-270A-9 CF₃ Cl Cl CH₃ H C.I-271 A-1 H H CF₃ CH₃ H C.I-272 A-2 H H CF₃ CH₃ HC.I-273 A-3 H H CF₃ CH₃ H C.I-274 A-4 H H CF₃ CH₃ H C.I-275 A-5 H H CF₃CH₃ H C.I-276 A-6 H H CF₃ CH₃ H C.I-277 A-7 H H CF₃ CH₃ H C.I-278 A-8 HH CF₃ CH₃ H C.I-279 A-9 H H CF₃ CH₃ H C.I-280 A-1 H Cl CF₃ CH₃ H C.I-281A-2 H Cl CF₃ CH₃ H C.I-282 A-3 H Cl CF₃ CH₃ H C.I-283 A-4 H Cl CF₃ CH₃ HC.I-284 A-5 H Cl CF₃ CH₃ H C.I-285 A-6 H Cl CF₃ CH₃ H C.I-286 A-7 H ClCF₃ CH₃ H C.I-287 A-8 H Cl CF₃ CH₃ H C.I-288 A-9 H Cl CF₃ CH₃ H C.I-289A-1 Cl H CF₃ CH₃ H C.I-290 A-2 Cl H CF₃ CH₃ H C.I-291 A-3 Cl H CF₃ CH₃ HC.I-292 A-4 Cl H CF₃ CH₃ H C.I-293 A-5 Cl H CF₃ CH₃ H C.I-294 A-6 Cl HCF₃ CH₃ H C.I-295 A-7 Cl H CF₃ CH₃ H C.I-296 A-8 Cl H CF₃ CH₃ H C.I-297A-9 Cl H CF₃ CH₃ H C.I-298 A-1 Cl Cl CF₃ CH₃ H C.I-299 A-2 Cl Cl CF₃ CH₃H C.I-300 A-3 Cl Cl CF₃ CH₃ H C.I-301 A-4 Cl Cl CF₃ CH₃ H C.I-302 A-5 ClCl CF₃ CH₃ H C.I-303 A-6 Cl Cl CF₃ CH₃ H C.I-304 A-7 Cl Cl CF₃ CH₃ HC.I-305 A-8 Cl Cl CF₃ CH₃ H C.I-306 A-9 Cl Cl CF₃ CH₃ H C.I-307 A-1 CF₃H CF₃ CH₃ H C.I-308 A-2 CF₃ H CF₃ CH₃ H C.I-309 A-3 CF₃ H CF₃ CH₃ HC.I-310 A-4 CF₃ H CF₃ CH₃ H C.I-311 A-5 CF₃ H CF₃ CH₃ H C.I-312 A-6 CF₃H CF₃ CH₃ H C.I-313 A-7 CF₃ H CF₃ CH₃ H C.I-314 A-8 CF₃ H CF₃ CH₃ HC.I-315 A-9 CF₃ H CF₃ CH₃ H C.I-316 A-1 CF₃ Cl CF₃ CH₃ H C.I-317 A-2 CF₃Cl CF₃ CH₃ H C.I-318 A-3 CF₃ Cl CF₃ CH₃ H C.I-319 A-4 CF₃ Cl CF₃ CH₃ HC.I-320 A-5 CF₃ Cl CF₃ CH₃ H C.I-321 A-6 CF₃ Cl CF₃ CH₃ H C.I-322 A-7CF₃ Cl CF₃ CH₃ H C.I-323 A-8 CF₃ Cl CF₃ CH₃ H C.I-324 A-9 CF₃ Cl CF₃ CH₃H C.I-325 A-1 H H H CH═CH—CH═CH C.I-326 A-2 H H H CH═CH—CH═CH C.I-327A-3 H H H CH═CH—CH═CH C.I-328 A-4 H H H CH═CH—CH═CH C.I-329 A-5 H H HCH═CH—CH═CH C.I-330 A-6 H H H CH═CH—CH═CH C.I-331 A-7 H H H CH═CH—CH═CHC.I-332 A-8 H H H CH═CH—CH═CH C.I-333 A-9 H H H CH═CH—CH═CH C.I-334 A-1H Cl H CH═CH—CH═CH C.I-335 A-2 H Cl H CH═CH—CH═CH C.I-336 A-3 H Cl HCH═CH—CH═CH C.I-337 A-4 H Cl H CH═CH—CH═CH C.I-338 A-5 H Cl HCH═CH—CH═CH C.I-339 A-6 H Cl H CH═CH—CH═CH C.I-340 A-7 H Cl HCH═CH—CH═CH C.I-341 A-8 H Cl H CH═CH—CH═CH C.I-342 A-9 H Cl HCH═CH—CH═CH C.I-343 A-1 Cl H H CH═CH—CH═CH C.I-344 A-2 Cl H HCH═CH—CH═CH C.I-345 A-3 Cl H H CH═CH—CH═CH C.I-346 A-4 Cl H HCH═CH—CH═CH C.I-347 A-5 Cl H H CH═CH—CH═CH C.I-348 A-6 Cl H HCH═CH—CH═CH C.I-349 A-7 Cl H H CH═CH—CH═CH C.I-350 A-8 Cl H HCH═CH—CH═CH C.I-351 A-9 Cl H H CH═CH—CH═CH C.I-352 A-1 Cl Cl HCH═CH—CH═CH C.I-353 A-2 Cl Cl H CH═CH—CH═CH C.I-354 A-3 Cl Cl HCH═CH—CH═CH C.I-355 A-4 Cl Cl H CH═CH—CH═CH C.I-356 A-5 Cl Cl HCH═CH—CH═CH C.I-357 A-6 Cl Cl H CH═CH—CH═CH C.I-358 A-7 Cl Cl HCH═CH—CH═CH C.I-359 A-8 Cl Cl H CH═CH—CH═CH C.I-360 A-9 Cl Cl HCH═CH—CH═CH C.I-361 A-1 CF₃ H H CH═CH—CH═CH C.I-362 A-2 CF₃ H HCH═CH—CH═CH C.I-363 A-3 CF₃ H H CH═CH—CH═CH C.I-364 A-4 CF₃ H HCH═CH—CH═CH C.I-365 A-5 CF₃ H H CH═CH—CH═CH C.I-366 A-6 CF₃ H HCH═CH—CH═CH C.I-367 A-7 CF₃ H H CH═CH—CH═CH C.I-368 A-8 CF₃ H HCH═CH—CH═CH C.I-369 A-9 CF₃ H H CH═CH—CH═CH C.I-370 A-1 CF₃ Cl HCH═CH—CH═CH C.I-371 A-2 CF₃ Cl H CH═CH—CH═CH C.I-372 A-3 CF₃ Cl HCH═CH—CH═CH C.I-373 A-4 CF₃ Cl H CH═CH—CH═CH C.I-374 A-5 CF₃ Cl HCH═CH—CH═CH C.I-375 A-6 CF₃ Cl H CH═CH—CH═CH C.I-376 A-7 CF₃ Cl HCH═CH—CH═CH C.I-377 A-8 CF₃ Cl H CH═CH—CH═CH C.I-378 A-9 CF₃ Cl HCH═CH—CH═CH C.I-379 A-1 H H Cl CH═CH—CH═CH C.I-380 A-2 H H ClCH═CH—CH═CH C.I-381 A-3 H H Cl CH═CH—CH═CH C.I-382 A-4 H H ClCH═CH—CH═CH C.I-383 A-5 H H Cl CH═CH—CH═CH C.I-384 A-6 H H ClCH═CH—CH═CH C.I-385 A-7 H H Cl CH═CH—CH═CH C.I-386 A-8 H H ClCH═CH—CH═CH C.I-387 A-9 H H Cl CH═CH—CH═CH C.I-388 A-1 H Cl ClCH═CH—CH═CH C.I-389 A-2 H Cl Cl CH═CH—CH═CH C.I-390 A-3 H Cl ClCH═CH—CH═CH C.I-391 A-4 H Cl Cl CH═CH—CH═CH C.I-392 A-5 H Cl ClCH═CH—CH═CH C.I-393 A-6 H Cl Cl CH═CH—CH═CH C.I-394 A-7 H Cl ClCH═CH—CH═CH C.I-395 A-8 H Cl Cl CH═CH—CH═CH C.I-396 A-9 H Cl ClCH═CH—CH═CH C.I-397 A-1 Cl H Cl CH═CH—CH═CH C.I-398 A-2 Cl H ClCH═CH—CH═CH C.I-399 A-3 Cl H Cl CH═CH—CH═CH C.I-400 A-4 Cl H ClCH═CH—CH═CH C.I-401 A-5 Cl H Cl CH═CH—CH═CH C.I-402 A-6 Cl H ClCH═CH—CH═CH C.I-403 A-7 Cl H Cl CH═CH—CH═CH C.I-404 A-8 Cl H ClCH═CH—CH═CH C.I-405 A-9 Cl H Cl CH═CH—CH═CH C.I-406 A-1 Cl Cl ClCH═CH—CH═CH C.I-407 A-2 Cl Cl Cl CH═CH—CH═CH C.I-408 A-3 Cl Cl ClCH═CH—CH═CH C.I-409 A-4 Cl Cl Cl CH═CH—CH═CH C.I-410 A-5 Cl Cl ClCH═CH—CH═CH C.I-411 A-6 Cl Cl Cl CH═CH—CH═CH C.I-412 A-7 Cl Cl ClCH═CH—CH═CH C.I-413 A-8 Cl Cl Cl CH═CH—CH═CH C.I-414 A-9 Cl Cl ClCH═CH—CH═CH C.I-415 A-1 CF₃ H Cl CH═CH—CH═CH C.I-416 A-2 CF₃ H ClCH═CH—CH═CH C.I-417 A-3 CF₃ H Cl CH═CH—CH═CH C.I-418 A-4 CF₃ H ClCH═CH—CH═CH C.I-419 A-5 CF₃ H Cl CH═CH—CH═CH C.I-420 A-6 CF₃ H ClCH═CH—CH═CH C.I-421 A-7 CF₃ H Cl CH═CH—CH═CH C.I-422 A-8 CF₃ H ClCH═CH—CH═CH C.I-423 A-9 CF₃ H Cl CH═CH—CH═CH C.I-424 A-1 CF₃ Cl ClCH═CH—CH═CH C.I-425 A-2 CF₃ Cl Cl CH═CH—CH═CH C.I-426 A-3 CF₃ Cl ClCH═CH—CH═CH C.I-427 A-4 CF₃ Cl Cl CH═CH—CH═CH C.I-428 A-5 CF₃ Cl ClCH═CH—CH═CH C.I-429 A-6 CF₃ Cl Cl CH═CH—CH═CH C.I-430 A-7 CF₃ Cl ClCH═CH—CH═CH C.I-431 A-8 CF₃ Cl Cl CH═CH—CH═CH C.I-432 A-9 CF₃ Cl ClCH═CH—CH═CH C.I-433 A-1 H H CF₃ CH═CH—CH═CH C.I-434 A-2 H H CF₃CH═CH—CH═CH C.I-435 A-3 H H CF₃ CH═CH—CH═CH C.I-436 A-4 H H CF₃CH═CH—CH═CH C.I-437 A-5 H H CF₃ CH═CH—CH═CH C.I-438 A-6 H H CF₃CH═CH—CH═CH C.I-439 A-7 H H CF₃ CH═CH—CH═CH C.I-440 A-8 H H CF₃CH═CH—CH═CH C.I-441 A-9 H H CF₃ CH═CH—CH═CH C.I-442 A-1 H Cl CF₃CH═CH—CH═CH C.I-443 A-2 H Cl CF₃ CH═CH—CH═CH C.I-444 A-3 H Cl CF₃CH═CH—CH═CH C.I-445 A-4 H Cl CF₃ CH═CH—CH═CH C.I-446 A-5 H Cl CF₃CH═CH—CH═CH C.I-447 A-6 H Cl CF₃ CH═CH—CH═CH C.I-448 A-7 H Cl CF₃CH═CH—CH═CH C.I-449 A-8 H Cl CF₃ CH═CH—CH═CH C.I-450 A-9 H Cl CF₃CH═CH—CH═CH C.I-451 A-1 Cl H CF₃ CH═CH—CH═CH C.I-452 A-2 Cl H CF₃CH═CH—CH═CH C.I-453 A-3 Cl H CF₃ CH═CH—CH═CH C.I-454 A-4 Cl H CF₃CH═CH—CH═CH C.I-455 A-5 Cl H CF₃ CH═CH—CH═CH C.I-456 A-6 Cl H CF₃CH═CH—CH═CH C.I-457 A-7 Cl H CF₃ CH═CH—CH═CH C.I-458 A-8 Cl H CF₃CH═CH—CH═CH C.I-459 A-9 Cl H CF₃ CH═CH—CH═CH C.I-460 A-1 Cl Cl CF₃CH═CH—CH═CH C.I-461 A-2 Cl Cl CF₃ CH═CH—CH═CH C.I-462 A-3 Cl Cl CF₃CH═CH—CH═CH C.I-463 A-4 Cl Cl CF₃ CH═CH—CH═CH C.I-464 A-5 Cl Cl CF₃CH═CH—CH═CH C.I-465 A-6 Cl Cl CF₃ CH═CH—CH═CH C.I-466 A-7 Cl Cl CF₃CH═CH—CH═CH C.I-467 A-8 Cl Cl CF₃ CH═CH—CH═CH C.I-468 A-9 Cl Cl CF₃CH═CH—CH═CH C.I-469 A-1 CF₃ H CF₃ CH═CH—CH═CH C.I-470 A-2 CF₃ H CF₃CH═CH—CH═CH C.I-471 A-3 CF₃ H CF₃ CH═CH—CH═CH C.I-472 A-4 CF₃ H CF₃CH═CH—CH═CH C.I-473 A-5 CF₃ H CF₃ CH═CH—CH═CH C.I-474 A-6 CF₃ H CF₃CH═CH—CH═CH C.I-475 A-7 CF₃ H CF₃ CH═CH—CH═CH C.I-476 A-8 CF₃ H CF₃CH═CH—CH═CH C.I-477 A-9 CF₃ H CF₃ CH═CH—CH═CH C.I-478 A-1 CF₃ Cl CF₃CH═CH—CH═CH C.I-479 A-2 CF₃ Cl CF₃ CH═CH—CH═CH C.I-480 A-3 CF₃ Cl CF₃CH═CH—CH═CH C.I-481 A-4 CF₃ Cl CF₃ CH═CH—CH═CH C.I-482 A-5 CF₃ Cl CF₃CH═CH—CH═CH C.I-483 A-6 CF₃ Cl CF₃ CH═CH—CH═CH C.I-484 A-7 CF₃ Cl CF₃CH═CH—CH═CH C.I-485 A-8 CF₃ Cl CF₃ CH═CH—CH═CH C.I-486 A-9 CF₃ Cl CF₃CH═CH—CH═CH

The examples of compounds I of formula I of table C.I.1 include theirtautomers, racemic mixtures, individual pure enantiomers anddiasteroemers and their optically active mixtures.

General Preparation Methods of Compounds of Formula I

The active compounds I can be prepared according to methods as describedin WO2005/085216, WO2007/074789 or in WO2007/079162.

Preferred Active Compounds II Selected from Group A

With respect to their use in the pesticidal mixtures of the presentinvention, particular preference is given to the compounds C.II aslisted in the paragraphs below.

With regard to the use in a pesticidal mixture of the present invention,the compound II selected from group A.1 as defined above is preferablytriazemate or primicarb.

With regard to the use in a pesticidal mixture of the present invention,the compound II selected from group A.2 as defined above is preferablyendosulfan,N-Ethyl-2,2-dimethylpropionamide-2-(2,6-dichloro-α.α.α-trifluoro-p-tolyl)hydrazon,N-Ethyl-2,2-dichloro-1-methylcyclopropane-carboxamide-2-(2,6-dichloro-α.α.α-trifluoro-p-tolyl)hydrazon, acetoprole, ethiprole, fipronil, pyrafluprole, pyriprole orvaniliprole or the phenylpyrazole compound II.A^(2.1).

More preferably the compound II isN-Ethyl-2,2-dimethylpropionamide-2-(2,6-dichloro-α.α.α-trifluoro-p-tolyl)hydrazon,N-Ethyl-2,2-dichloro-1-methylcyclopropane-carboxamide-2-(2,6-dichloro-α.α.α-trifluoro-p-tolyl)hydrazon, acetoprole or fipronil.

With regard to the use in a pesticidal mixture of the present invention,the compound II selected from group A.3 as defined above is preferablyallethrin, bifenthrin, cyfluthrin, lambda-cyhalothrin, cypermethrin,alpha-cypermethrin, beta-cypermethrin, zeta-cypermethrin, deltamethrin,etofenprox, fenpropathrin, fenvalerate, flucythrinate, tau-fluvalinate,silafluofen or tralomethrin.

More preferably the compound II is alpha-cypermethrin or deltamethrin.

With regard to the use in a pesticidal mixture of the present invention,the compound II selected from group A.4 as defined above is preferablythiocyclam or from the class of neonicotinoids acteamiprid,chlothianidin, dinotefuran, imidacloprid, nitenpyram, thiacloprid,thiamethoxam and AKD-1022; or the allosteric nicotinic acteylcholinereceptor agonist spinosad.

More preferably the compound II is clothianidine, imidacloprid orthiamethoxam.

With regard to the use in a pesticidal mixture of the present invention,the compound II selected from group A.5 as defined above is preferablyabamectin, emamectin benzoate, lepimectin or milbemectin.

More preferably the compound II is abamectin.

With regard to the use in a pesticidal mixture of the present invention,the compound II selected from group A.7 as defined above is preferablydiafenthiuron.

With regard to the use in a pesticidal mixture of the present invention,the compound II selected from group A.8 as defined above is preferablybuprofezin.

With regard to the use in a pesticidal mixture of the present invention,the compound II selected from group A.10 as defined above is preferablypyridaben or flufenerim.

With regard to the use in a pesticidal mixture of the present invention,the compound II selected from group A.11 as defined above is preferablyindoxacarb or metaflumizone. More preferably the compound II ismetaflumizone.

With regard to the use in a pesticidal mixture of the present invention,the compound II selected from group A.12 as defined above is preferablyspirodiclofen, spiromesifen or spirotetramat.

More preferably the compound II is spiromesifen or spirotetramat.

With regard to the use in a pesticidal mixture of the present invention,the compound II selected from group A.13 as defined above is preferablyamitraz, flonicamid, flubendiamine, pymetrozine, pyridalyl,pyrifluquinazon, chlorantraniliproler, the anthranil compoundII.A^(13.1) or the sulfoximine compounds II.A^(13.2), II.A^(13.3) orII.A^(13.4).

More preferably the compound II is flonicamid, pymetrozine,pyrifluquinazon, chlorantraniliprole or the anthranil compoundII.A^(13.1).

Especially preferred are pesticidal mixtures containingN-Ethyl-2,2-dimethylpropionamide-2-(2,6-dichloro-α.α.α-trifluoro-p-tolyl)hydrazon as compound II.

Especially preferred are pesticidal mixtures containingN-Ethyl-2,2-dichloro-1-methylcyclopropane-carboxamide-2-(2,6-dichloro-α.α.α-trifluoro-p-tolyl)hydrazon as compound II.

Especially preferred are pesticidal mixtures containing acetoprole ascompound II.

Especially preferred are pesticidal mixtures containing fipronil ascompound II.

Especially preferred are pesticidal mixtures containingalpha-cypermethrin as compound II.

Especially preferred are pesticidal mixtures containing clothianidin ascompound II.

Especially preferred are pesticidal mixtures containing imidacloprid ascompound II.

Especially preferred are pesticidal mixtures containing thiamethoxam ascompound II.

Especially preferred are pesticidal mixtures containing pymetrozine ascompound II.

Especially preferred are pesticidal mixtures containing flonicamid ascompound II.

Especially preferred are pesticidal mixtures containing spiromesifen ascompound II.

Especially preferred are pesticidal mixtures containing spirotetramat ascompound II.

Especially preferred are pesticidal mixtures containing pyrifluquinazonas compound II.

Especially preferred are pesticidal mixtures containingchlorantraniliprole as compound II.

Especially preferred are pesticidal mixtures containing theanthranilamid compound II.A^(13.1)

as compound II.

Especially preferred are pesticidal mixtures containing the sulfoximinecompound

as compound II.

Especially preferred are pesticidal mixtures containing the sulfoximinecompound II.A^(13.3)

as compound II.

Especially preferred are pesticidal mixtures containing the sulfoximinecompound II.A^(13.4)

as compound II.

Preferred Mixtures According to the Invention

Especially preferred are inventive mixtures wherein the compound II ofgroup A is acetoprol and the compound I of formula I is a compound ofTable C.I.1.

Especially preferred are inventive mixtures wherein the compound II ofgroup A is fipronil and the compound I of formula I is a compound ofTable C.I.1.

Especially preferred are inventive mixtures wherein the compound II ofgroup A isN-Ethyl-2,2-dimethylpropionamide-2-(2,6-dichloro-α.α.α-trifluoro-p-tolyl)hydrazon and the compound I of formula I is a compound of Table C.I.1.

Especially preferred are inventive mixtures wherein the compound II ofgroup A isN-Ethyl-2,2-dichloro-1-methylcyclopropane-carboxamide-2-(2,6-dichloro-α.α.α-trifluoro-p-tolyl)hydrazon and the compound I of formula I is a compound of Table C.I.1.

Especially preferred are inventive mixtures wherein the compound II ofgroup A is alpha-cypermethrin and the compound I of formula I is acompound of Table C.I.1.

Especially preferred are inventive mixtures wherein the compound II ofgroup A is deltamethrin and the compound I of formula I is a compound ofTable C.I.1.

Especially preferred are inventive mixtures wherein the compound II ofgroup A is clothianidin and the compound I of formula I is a compound ofTable C.I.1.

Especially preferred are inventive mixtures wherein the compound II ofgroup A is imidacloprid and the compound I of formula I is a compound ofTable C.I.1.

Especially preferred are inventive mixtures wherein the compound II ofgroup A is thiamethoxam and the compound I of formula I is a compound ofTable C.I.1.

Especially preferred are inventive mixtures wherein the compound II ofgroup A is abamectin and the compound I of formula I is a compound ofTable C.I.1.

Especially preferred are inventive mixtures wherein the compound II ofgroup A is pymetrozine and the compound I of formula I is a compound ofTable C.I.1.

Especially preferred are inventive mixtures wherein the compound II ofgroup A is flonicamid and the compound I of formula I is a compound ofTable C.I.1.

Especially preferred are inventive mixtures wherein the compound II ofgroup A is diafenthiuron and the compound I of formula I is a compoundof Table C.I.1.

Especially preferred are inventive mixtures wherein the compound II ofgroup A is buprofezin and the compound I of formula I is a compound ofTable C.I.1.

Especially preferred are inventive mixtures wherein the compound II ofgroup A is pyridaben and the compound I of formula I is a compound ofTable C.I.1.

Especially preferred are inventive mixtures wherein the compound II ofgroup A is flufenerim and the compound I of formula I is a compound ofTable C.I.1.

Especially preferred are inventive mixtures wherein the compound II ofgroup A is metaflumizone and the compound I of formula I is a compoundof Table C.I.1.

Especially preferred are inventive mixtures wherein the compound II ofgroup A is spiromesifen and the compound I of formula I is a compound ofTable C.I.1.

Especially preferred are inventive mixtures wherein the compound II ofgroup A is spirotetramat and the compound I of formula I is a compoundof Table C.I.1.

Especially preferred are inventive mixtures wherein the compound II ofgroup A is pyrifluquinazon and the compound I of formula I is a compoundof Table C.I.1.

Especially preferred are inventive mixtures wherein the compound II ofgroup A is chlorantraniliprole and the compound I of formula I is acompound of Table C.I.1.

Especially preferred are inventive mixtures wherein the compound II ofgroup A is the anthranilamid compound II.A^(13.1) and the compound I offormula I is a compound of Table C.I.1.

Especially preferred are inventive mixtures wherein the compound II ofgroup A is the sulfoximine compound II.A^(13.2) and the compound I offormula I is a compound of Table C.I.1.

Especially preferred are inventive mixtures wherein the compound II ofgroup A is the sulfoximine compound II.A^(13.3) and the compound I offormula I is a compound of Table C.I.1.

Especially preferred are inventive mixtures wherein the compound II ofgroup A is the sulfoximine compound II.A^(13.4) and the compound I offormula I is a compound of Table C.I.1.

The following table M represents preferred combinations of the activecompounds I of formula I as defined in table C.I.1 and the activecompounds II of group A in mixtures according to the invention:

TABLE M Mixture Compound I Compound-II Mixture Compound I Compound IIM.1 C.I-37 acetoprole M.221 C.I-37 diafenthiuron M.2 C.I-40 acetoproleM.222 C.I-40 diafenthiuron M.3 C.I-73 acetoprole M.223 C.I-73diafenthiuron M.4 C.I-76 acetoprole M.224 C.I-76 diafenthiuron M.5C.I-145 acetoprole M.225 C.I-145 diafenthiuron M.6 C.I-148 acetoproleM.226 C.I-148 diafenthiuron M.7 C.I-199 acetoprole M.227 C.I-199diafenthiuron M.8 C.I-202 acetoprole M.228 C.I-202 diafenthiuron M.9C.I-235 acetoprole M.229 C.I-235 diafenthiuron M.10 C.I-238 acetoproleM.230 C.I-238 diafenthiuron M.11 C.I.240 acetoprole M.231 C.I.240diafenthiuron M.12 C.I-244 acetoprole M.232 C.I-244 diafenthiuron M.13C.I-247 acetoprole M.233 C.I-247 diafenthiuron M.14 C.I-307 acetoproleM.234 C.I-307 diafenthiuron M.15 C.I-310 acetoprole M.235 C.I-310diafenthiuron M.16 C.I-361 acetoprole M.236 C.I-361 diafenthiuron M.17C.I-364 acetoprole M.237 C.I-364 diafenthiuron M.18 C.I-397 acetoproleM.238 C.I-397 diafenthiuron M.19 C.I-400 acetoprole M.239 C.I-400diafenthiuron M.20 C.I-406 acetoprole M.240 C.I-406 diafenthiuron M.21C.I-409 acetoprole M.241 C.I-409 diafenthiuron M.22 C.I-469 acetoproleM.242 C.I-469 diafenthiuron M.23 C.I-472 acetoprole M.243 C.I-472diafenthiuron M.24 C.I-37 fipronil M.244 C.I-37 buprofezin M.25 C.I-40fipronil M.245 C.I-40 buprofezin M.26 C.I-73 fipronil M.246 C.I-73buprofezin M.27 C.I-76 fipronil M.247 C.I-76 buprofezin M.28 C.I-145fipronil M.248 C.I-145 buprofezin M.29 C.I-148 fipronil M.249 C.I-148buprofezin M.30 C.I-199 fipronil M.250 C.I-199 buprofezin M.31 C.I-202fipronil M.251 C.I-202 buprofezin M.32 C.I-235 fipronil M.252 C.I-235buprofezin M.33 C.I-238 fipronil M.253 C.I-238 buprofezin M.34 C.I.240fipronil M.254 C.I.240 buprofezin M.35 C.I-244 fipronil M.255 C.I-244buprofezin M.36 C.I-247 fipronil M.256 C.I-247 buprofezin M.37 C.I-307fipronil M.257 C.I-307 buprofezin M.38 C.I-310 fipronil M.258 C.I-310buprofezin M.39 C.I-361 fipronil M.259 C.I-361 buprofezin M.40 C.I-364fipronil M.260 C.I-364 buprofezin M.41 C.I-397 fipronil M.261 C.I-397buprofezin M.42 C.I-400 fipronil M.262 C.I-400 buprofezin M.43 C.I-406fipronil M.263 C.I-406 buprofezin M.44 C.I-409 fipronil M.264 C.I-409buprofezin M.45 C.I-469 fipronil M.265 C.I-469 buprofezin M.46 C.I-472fipronil M.266 C.I-472 buprofezin M.47 C.I-37 imidacloprid M.267 C.I-37pyridaben M.48 C.I-40 imidacloprid M.268 C.I-40 pyridaben M.49 C.I-73imidacloprid M.269 C.I-73 pyridaben M.50 C.I-76 imidacloprid M.270C.I-76 pyridaben M.51 C.I-145 imidacloprid M.271 C.I-145 pyridaben M.52C.I-148 imidacloprid M.272 C.I-148 pyridaben M.53 C.I-199 imidaclopridM.273 C.I-199 pyridaben M.54 C.I-202 imidacloprid M.274 C.I-202pyridaben M.55 C.I-235 imidacloprid M.275 C.I-235 pyridaben M.56 C.I-238imidacloprid M.276 C.I-238 pyridaben M.57 C.I.240 imidacloprid M.277C.I.240 pyridaben M.58 C.I-244 imidacloprid M.278 C.I-244 pyridaben M.59C.I-247 imidacloprid M.279 C.I-247 pyridaben M.60 C.I-307 imidaclopridM.280 C.I-307 pyridaben M.61 C.I-310 imidacloprid M.281 C.I-310pyridaben M.62 C.I-361 imidacloprid M.282 C.I-361 pyridaben M.63 C.I-364imidacloprid M.283 C.I-364 pyridaben M.64 C.I-397 imidacloprid M.284C.I-397 pyridaben M.65 C.I-400 imidacloprid M.285 C.I-400 pyridaben M.66C.I-406 imidacloprid M.286 C.I-406 pyridaben M.67 C.I-409 imidaclopridM.287 C.I-409 pyridaben M.68 C.I-469 imidacloprid M.288 C.I-469pyridaben M.69 C.I-472 imidacloprid M.289 C.I-472 pyridaben M.70 C.I-37abamectin M.290 C.I-37 spiromesifen M.71 C.I-40 abamectin M.291 C.I-40spiromesifen M.72 C.I-73 abamectin M.292 C.I-73 spiromesifen M.73 C.I-76abamectin M.293 C.I-76 spiromesifen M.74 C.I-145 abamectin M.294 C.I-145spiromesifen M.75 C.I-148 abamectin M.295 C.I-148 spiromesifen M.76C.I-199 abamectin M.296 C.I-199 spiromesifen M.77 C.I-202 abamectinM.297 C.I-202 spiromesifen M.78 C.I-235 abamectin M.298 C.I-235spiromesifen M.79 C.I-238 abamectin M.299 C.I-238 spiromesifen M.80C.I.240 abamectin M.300 C.I.240 spiromesifen M.81 C.I-244 abamectinM.301 C.I-244 spiromesifen M.82 C.I-247 abamectin M.302 C.I-247spiromesifen M.83 C.I-307 abamectin M.303 C.I-307 spiromesifen M.84C.I-310 abamectin M.304 C.I-310 spiromesifen M.85 C.I-361 abamectinM.305 C.I-361 spiromesifen M.86 C.I-364 abamectin M.306 C.I-364spiromesifen M.87 C.I-397 abamectin M.307 C.I-397 spiromesifen M.88C.I-400 abamectin M.308 C.I-400 spiromesifen M.89 C.I-406 abamectinM.309 C.I-406 spiromesifen M.90 C.I-409 abamectin M.310 C.I-409spiromesifen M.91 C.I-469 abamectin M.311 C.I-469 spiromesifen M.92C.I-472 abamectin M.312 C.I-472 spiromesifen M.93 C.I-37 anthranilamidM.313 C.I-37 chlorantraniliprole II.A^(13.1) M.94 C.I-40 anthranilamidM.314 C.I-40 chlorantraniliprole II.A^(13.1) M.95 C.I-73 anthranilamidM.315 C.I-73 chlorantraniliprole II.A^(13.1) M.96 C.I-76 anthranilamidM.316 C.I-76 chlorantraniliprole II.A^(13.1) M.97 C.I-145 anthranilamidM.317 C.I-145 chlorantraniliprole II.A^(13.1) M.98 C.I-148 anthranilamidM.318 C.I-148 chlorantraniliprole II.A^(13.1) M.99 C.I-199 anthranilamidM.319 C.I-199 chlorantraniliprole II.A^(13.1) M.100 C.I-202anthranilamid M.320 C.I-202 chlorantraniliprole II.A^(13.1) M.101C.I-235 anthranilamid M.321 C.I-235 chlorantraniliprole II.A^(13.1)M.102 C.I-238 anthranilamid M.322 C.I-238 chlorantraniliproleII.A^(13.1) M.103 C.I.240 anthranilamid M.323 C.I.240chlorantraniliprole II.A^(13.1) M.104 C.I-244 anthranilamid M.324C.I-244 chlorantraniliprole II.A^(13.1) M.105 C.I-247 anthranilamidM.325 C.I-247 chlorantraniliprole II.A^(13.1) M.106 C.I-307anthranilamid M.326 C.I-307 chlorantraniliprole II.A^(13.1) M.107C.I-310 anthranilamid M.327 C.I-310 chlorantraniliprole II.A^(13.1)M.108 C.I-361 anthranilamid M.328 C.I-361 chlorantraniliproleII.A^(13.1) M.109 C.I-364 anthranilamid M.329 C.I-364chlorantraniliprole II.A^(13.1) M.110 C.I-397 anthranilamid M.330C.I-397 chlorantraniliprole II.A^(13.1) M.111 C.I-400 anthranilamidM.331 C.I-400 chlorantraniliprole II.A^(13.1) M.112 C.I-406anthranilamid M.332 C.I-406 chlorantraniliprole II.A^(13.1) M.113C.I-409 anthranilamid M.333 C.I-409 chlorantraniliprole II.A^(13.1)M.114 C.I-469 anthranilamid M.334 C.I-469 chlorantraniliproleII.A^(13.1) M.115 C.I-472 anthranilamid M.335 C.I-472chlorantraniliprole II.A^(13.1) M.116 C.I-37 deltamethrin M.336 C.I-37flufenerim M.117 C.I-40 deltamethrin M.337 C.I-40 flufenerim M.118C.I-73 deltamethrin M.338 C.I-73 flufenerim M.119 C.I-76 deltamethrinM.339 C.I-76 flufenerim M.120 C.I-145 deltamethrin M.340 C.I-145flufenerim M.121 C.I-148 deltamethrin M.341 C.I-148 flufenerim M.122C.I-199 deltamethrin M.342 C.I-199 flufenerim M.123 C.I-202 deltamethrinM.343 C.I-202 flufenerim M.124 C.I-235 deltamethrin M.344 C.I-235flufenerim M.125 C.I-238 deltamethrin M.345 C.I-238 flufenerim M.126C.I.240 deltamethrin M.346 C.I.240 flufenerim M.127 C.I-244 deltamethrinM.347 C.I-244 flufenerim M.128 C.I-247 deltamethrin M.348 C.I-247flufenerim M.129 C.I-307 deltamethrin M.349 C.I-307 flufenerim M.130C.I-310 deltamethrin M.350 C.I-310 flufenerim M.131 C.I-361 deltamethrinM.351 C.I-361 flufenerim M.132 C.I-364 deltamethrin M.352 C.I-364flufenerim M.133 C.I-397 deltamethrin M.353 C.I-397 flufenerim M.134C.I-400 deltamethrin M.354 C.I-400 flufenerim M.135 C.I-406 deltamethrinM.355 C.I-406 flufenerim M.136 C.I-409 deltamethrin M.356 C.I-409flufenerim M.137 C.I-469 deltamethrin M.357 C.I-469 flufenerim M.138C.I-472 deltamethrin M.358 C.I-472 flufenerim M.139 C.I-37 metaflumizoneM.359 C.I-37 α-cypermethrin M.140 C.I-40 metaflumizone M.360 C.I-40α-cypermethrin M.141 C.I-73 metaflumizone M.361 C.I-73 α-cypermethrinM.142 C.I-76 metaflumizone M.362 C.I-76 α-cypermethrin M.143 C.I-145metaflumizone M.363 C.I-145 α-cypermethrin M.144 C.I-148 metaflumizoneM.364 C.I-148 α-cypermethrin M.145 C.I-199 metaflumizone M.365 C.I-199α-cypermethrin M.146 C.I-202 metaflumizone M.366 C.I-202 α-cypermethrinM.147 C.I-235 metaflumizone M.367 C.I-235 α-cypermethrin M.148 C.I-238metaflumizone M.368 C.I-238 α-cypermethrin M.149 C.I.240 metaflumizoneM.369 C.I.240 α-cypermethrin M.150 C.I-244 metaflumizone M.370 C.I-244α-cypermethrin M.151 C.I-247 metaflumizone M.371 C.I-247 α-cypermethrinM.152 C.I-307 metaflumizone M.372 C.I-307 α-cypermethrin M.153 C.I-310metaflumizone M.373 C.I-310 α-cypermethrin M.154 C.I-361 metaflumizoneM.374 C.I-361 α-cypermethrin M.155 C.I-364 metaflumizone M.375 C.I-364α-cypermethrin M.156 C.I-397 metaflumizone M.376 C.I-397 α-cypermethrinM.157 C.I-400 metaflumizone M.377 C.I-400 α-cypermethrin M.158 C.I-406metaflumizone M.378 C.I-406 α-cypermethrin M.159 C.I-409 metaflumizoneM.379 C.I-409 α-cypermethrin M.160 C.I-469 metaflumizone M.380 C.I-469α-cypermethrin M.161 C.I-472 metaflumizone M.381 C.I-472 α-cypermethrinM.162 C.I-37 clothianidine M.382 C.I-37 thiamethoxam M.163 C.I-40clothianidine M.383 C.I-40 thiamethoxam M.164 C.I-73 clothianidine M.384C.I-73 thiamethoxam M.165 C.I-76 clothianidine M.385 C.I-76 thiamethoxamM.166 C.I-145 clothianidine M.386 C.I-145 thiamethoxam M.167 C.I-148clothianidine M.387 C.I-148 thiamethoxam M.168 C.I-199 clothianidineM.388 C.I-199 thiamethoxam M.169 C.I-202 clothianidine M.389 C.I-202thiamethoxam M.170 C.I-235 clothianidine M.390 C.I-235 thiamethoxamM.171 C.I-238 clothianidine M.391 C.I-238 thiamethoxam M.172 C.I.240clothianidine M.392 C.I.240 thiamethoxam M.173 C.I-244 clothianidineM.393 C.I-244 thiamethoxam M.174 C.I-247 clothianidine M.394 C.I-247thiamethoxam M.175 C.I-307 clothianidine M.395 C.I-307 thiamethoxamM.176 C.I-310 clothianidine M.396 C.I-310 thiamethoxam M.177 C.I-361clothianidine M.397 C.I-361 thiamethoxam M.178 C.I-364 clothianidineM.398 C.I-364 thiamethoxam M.179 C.I-397 clothianidine M.399 C.I-397thiamethoxam M.180 C.I-400 clothianidine M.400 C.I-400 thiamethoxamM.181 C.I-406 clothianidine M.401 C.I-406 thiamethoxam M.182 C.I-409clothianidine M.402 C.I-409 thiamethoxam M.183 C.I-469 clothianidineM.403 C.I-469 thiamethoxam M.184 C.I-472 clothianidine M.404 C.I-472thiamethoxam M.185 C.I-37 flonicamid M.405 C.I-37 spirotetramat M.186C.I-40 flonicamid M.406 C.I-40 spirotetramat M.187 C.I-73 flonicamidM.407 C.I-73 spirotetramat M.188 C.I-76 flonicamid M.408 C.I-76spirotetramat M.189 C.I-145 flonicamid M.409 C.I-145 spirotetramat M.190C.I-148 flonicamid M.410 C.I-148 spirotetramat M.191 C.I-199 flonicamidM.411 C.I-199 spirotetramat M.192 C.I-202 flonicamid M.412 C.I-202spirotetramat M.193 C.I-235 flonicamid M.413 C.I-235 spirotetramat M.194C.I-238 flonicamid M.414 C.I-238 spirotetramat M.195 C.I.240 flonicamidM.415 C.I.240 spirotetramat M.196 C.I-244 flonicamid M.416 C.I-244spirotetramat M.197 C.I-247 flonicamid M.417 C.I-247 spirotetramat M.198C.I-307 flonicamid M.418 C.I-307 spirotetramat M.199 C.I-310 flonicamidM.419 C.I-310 spirotetramat M.200 C.I-361 flonicamid M.420 C.I-361spirotetramat M.201 C.I-364 flonicamid M.421 C.I-364 spirotetramat M.202C.I-397 flonicamid M.422 C.I-397 spirotetramat M.203 C.I-400 flonicamidM.423 C.I-400 spirotetramat M.204 C.I-406 flonicamid M.424 C.I-406spirotetramat M.205 C.I-409 flonicamid M.425 C.I-409 spirotetramat M.206C.I-469 flonicamid M.426 C.I-469 spirotetramat M.207 C.I-472 flonicamidM.427 C.I-472 spirotetramat M.208 C.I-37 pymetrozine M.428 C.I-37pyrifluquinazone M.209 C.I-40 pymetrozine M.429 C.I-40 pyrifluquinazoneM.210 C.I-73 pymetrozine M.430 C.I-73 pyrifluquinazone M.211 C.I-76pymetrozine M.431 C.I-76 pyrifluquinazone M.212 C.I-145 pymetrozineM.432 C.I-145 pyrifluquinazone M.213 C.I-148 pymetrozine M.433 C.I-148pyrifluquinazone M.214 C.I-199 pymetrozine M.434 C.I-199pyrifluquinazone M.215 C.I-202 pymetrozine M.435 C.I-202pyrifluquinazone M.216 C.I-235 pymetrozine M.436 C.I-235pyrifluquinazone M.217 C.I-238 pymetrozine M.437 C.I-238pyrifluquinazone M.218 C.I.240 pymetrozine M.438 C.I.240pyrifluquinazone M.219 C.I-244 pymetrozine M.439 C.I-244pyrifluquinazone M.220 C.I-247 pymetrozine M.440 C.I-247pyrifluquinazone M.221 C.I-307 pymetrozine M.441 C.I-307pyrifluquinazone M.222 C.I-310 pymetrozine M.442 C.I-310pyrifluquinazone M.223 C.I-361 pymetrozine M.443 C.I-361pyrifluquinazone M.224 C.I-364 pymetrozine M.444 C.I-364pyrifluquinazone M.225 C.I-397 pymetrozine M.445 C.I-397pyrifluquinazone M.226 C.I-400 pymetrozine M.446 C.I-400pyrifluquinazone M.227 C.I-406 pymetrozine M.447 C.I-406pyrifluquinazone M.228 C.I-409 pymetrozine M.448 C.I-409pyrifluquinazone M.229 C.I-469 pymetrozine M.449 C.I-469pyrifluquinazone M.230 C.I-472 pymetrozine M.450 C.I-472pyrifluquinazone

Pests

The mixtures of the active compounds I and II, or the active compounds Iand II used simultaneously, that is jointly or separately, exhibitoutstanding action against pests from the following orders:

Insects from the order of the lepidopterans (Lepidoptera), for exampleAgrotis ypsilon, Agrotis segetum, Alabama argillacea, Anticarsiagemmatalis, Argyresthia conjugella, Autographa gamma, Bupalus piniarius,Cacoecia murinana, Capua reticulana, Cheimatobia brumata, Choristoneurafumiferana, Choristoneura occidentalis, Cirphis unipuncta, Cydiapomonella, Dendrolimus pini, Diaphania nitidalis, Diatraea grandiosella,Earias insulana, Elasmopalpus lignosellus, Eupoecilia ambiguella,Evetria bouliana, Feltia subterranea, Galleria mellonella, Grapholithafunebrana, Grapholitha molesta, Heliothis armigera, Heliothis virescens,Heliothis zea, Hellula undalis, Hibernia defoliaria, Hyphantria cunea,Hyponomeuta malinellus, Keiferia lycopersicella, Lambdina fiscellaria,Laphygma exigua, Leucoptera coffeella, Leucoptera scitella,Lithocolletis blancardella, Lobesia botrana, Loxostege sticticalis,Lymantria dispar, Lymantria monacha, Lyonetia clerkella, Malacosomaneustria, Mamestra brassicae, Orgyia pseudotsugata, Ostrinia nubilalis,Panolis flammea, Pectinophora gossypiella, Peridroma saucia, Phalerabucephala, Phthorimaea operculella, Phyllocnistis citrella, Pierisbrassicae, Plathypena scabra, Plutella xylostella, Pseudoplusiaincludens, Rhyacionia frustrana, Scrobipalpula absoluta, Sitotrogacerealella, Sparganothis pilleriana, Spodoptera frugiperda, Spodopteralittoralis, Spodoptera litura, Thaumatopoea pityocampa, Tortrixviridana, Trichoplusia ni and Zeiraphera canadensis,

beetles (Coleoptera), for example Agrilus sinuatus, Agriotes lineatus,Agriotes obscurus, Amphimallus solstitialis, Anisandrus dispar,Anthonomus grandis, Anthonomus pomorum, Aphthona euphoridae, Athoushaemorrhoidalis, Atomaria linearis, Blastophagus piniperda, Blitophagaundata, Bruchus rufimanus, Bruchus pisorum, Bruchus lentis, Byctiscusbetulae, Cassida nebulosa, Cerotoma trifurcata, Cetonia aurata,Ceuthorrhynchus assimilis, Ceuthorrhynchus napi, Chaetocnema tibialis,Conoderus vespertinus, Crioceris asparagi, Ctenicera ssp., Diabroticalongicornis, Diabrotica semipunctata, Diabrotica 12-punctata Diabroticaspeciosa, Diabrotica virgifera, Epilachna varivestis, Epitrixhirtipennis, Eutinobothrus brasiliensis, Hylobius abietis, Hyperabrunneipennis, Hypera postica, Ips typographus, Lema bilineata, Lemamelanopus, Leptinotarsa decemlineata, Limonius californicus,Lissorhoptrus oryzophilus, Melanotus communis, Meligethes aeneus,Melolontha hippocastani, Melolontha melolontha, Oulema oryzae,Ortiorrhynchus sulcatus, Otiorrhynchus ovatus, Phaedon cochleariae,Phyllobius pyri, Phyllotreta chrysocephala, Phyllophaga sp.,Phyllopertha horticola, Phyllotreta nemorum, Phyllotreta striolata,Popillia japonica, Sitona lineatus and Sitophilus granaria,flies, mosquitoes (Diptera), e.g. Aedes aegypti, Aedes albopictus, Aedesvexans, Anastrepha ludens, Anopheles maculipennis, Anopheles crucians,Anopheles albimanus, Anopheles gambiae, Anopheles freeborni, Anophelesleucosphyrus, Anopheles minimus, Anopheles quadrimaculatus, Calliphoravicina, Ceratitis capitata, Chrysomya bezziana, Chrysomya hominivorax,Chrysomya macellaria, Chrysops discalis, Chrysops silacea, Chrysopsatlanticus, Cochliomyia hominivorax, Contarinia sorghicola Cordylobiaanthropophaga, Culicoides furens, Culex pipiens, Culex nigripalpus,Culex quinquefasciatus, Culex tarsalis, Culiseta inornata, Culisetamelanura, Dacus cucurbitae, Dacus oleae, Dasineura brassicae, Deliaantique, Delia coarctata, Delia platura, Delia radicum, Dermatobiahominis, Fannia canicularis, Geomyza Tripunctata, Gasterophilusintestinalis, Glossina morsitans, Glossina palpalis, Glossina fuscipes,Glossina tachinoides, Haematobia irritans, Haplodiplosis equestris,Hippelates spp., Hylemyia platura, Hypoderma lineata, Leptoconopstorrens, Liriomyza sativae, Liriomyza trifolii, Lucilia caprina, Luciliacuprina, Lucilia sericata, Lycoria pectoralis, Mansonia titillanus,Mayetiola destructor, Musca domestica, Muscina stabulans, Oestrus ovis,Opomyza forum, Oscinella frit, Pegomya hysocyami, Phorbia antiqua,Phorbia brassicae, Phorbia coarctata, Phlebotomus argentipes, Psorophoracolumbiae, Psila rosae, Psorophora discolor, Prosimulium mixtum,Rhagoletis cerasi, Rhagoletis pomonella, Sarcophaga haemorrhoidalis,Sarcophaga sp., Simulium vittatum, Stomoxys calcitrans, Tabanus bovinus,Tabanus atratus, Tabanus lineola, and Tabanus similis, Tipula oleracea,and Tipula paludosathrips (Thysanoptera), e.g. Dichromothrips corbetti, Dichromothrips ssp,Frankliniella fusca, Frankliniella occidentalis, Frankliniella tritici,Scirtothrips citri, Thrips oryzae, Thrips palmi and Thrips tabaci,termites (Isoptera), e.g. Calotermes flavicollis, Leucotermes flavipes,Heterotermes aureus, Reticulitermes flavipes, Reticulitermes virginicus,Reticulitermes lucifugus, Termes natalensis, and Coptotermes formosanus,cockroaches (Blattaria-Blattodea), e.g. Blattella germanica, Blattellaasahinae, Periplaneta americana, Periplaneta japonica, Periplanetabrunnea, Periplaneta fuligginosa, Periplaneta australasiae, and Blattaorientalis,true bugs (Hemiptera), e.g. Acrosternum hilare, Blissus leucopterus,Cyrtopeltis notatus, Dysdercus cingulatus, Dysdercus intermedius,Eurygaster integriceps, Euschistus impictiventris, Leptoglossusphyllopus, Lygus lineolaris, Lygus pratensis, Nezara viridula, Piesmaquadrata, Solubea insularis, Thyanta perditor, Acyrthosiphon onobrychis,Adelges laricis, Aphidula nasturtii, Aphis fabae, Aphis forbesi, Aphispomi, Aphis gossypii, Aphis grossulariae, Aphis schneideri, Aphisspiraecola, Aphis sambuci, Acyrthosiphon pisum, Aulacorthum solani,Bemisia argentifolii, Brachycaudus cardui, Brachycaudus helichrysi,Brachycaudus persicae, Brachycaudus prunicola, Brevicoryne brassicae,Capitophorus horni, Cerosipha gossypii, Chaetosiphon fragaefolii,Cryptomyzus ribis, Dreyfusia nordmannianae, Dreyfusia piceae, Dysaphisradicola, Dysaulacorthum pseudosolani, Dysaphis plantaginea, Dysaphispyri, Empoasca fabae, Hyalopterus pruni, Hyperomyzus lactucae,Macrosiphum avenae, Macrosiphum euphorbiae, Macrosiphon rosae, Megouraviciae, Melanaphis pyrarius, Metopolophium dirhodum, Myzus persicae,Myzus ascalonicus, Myzus cerasi, Myzus varians, Nasonovia ribis-nigri,Nilaparvata lugens, Pemphigus bursarius, Perkinsiella saccharicida,Phorodon humuli, Psylla mali, Psylla pini, Rhopalomyzus ascalonicus,Rhopalosiphum maidis, Rhopalosiphum padi, Rhopalosiphum insertum,Sappaphis mala, Sappaphis mali, Schizaphis graminum, Schizoneuralanuginosa, Sitobion avenae, Trialeurodes vaporariorum, Toxopteraaurantiiand, Viteus vitifolii, Cimex lectularius, Cimex hemipterus,Reduvius senilis, Triatoma spp., and Arilus critatus.ants, bees, wasps, sawflies (Hymenoptera), e.g. Athalia rosae, Attacephalotes, Atta capiguara, Atta cephalotes, Atta laevigata, Attarobusta, Atta sexdens, Atta texana, Crematogaster spp., Hoplocampaminuta, Hoplocampa testudinea, Monomorium pharaonis, Solenopsisgeminata, Solenopsis invicta, Solenopsis richteri, Solenopsis xyloni,Pogonomyrmex barbatus, Pogonomyrmex californicus, Pheidole megacephala,Dasymutilla occidentalis, Bombus spp. Vespula squamosa, Paravespulavulgaris, Paravespula pennsylvanica, Paravespula germanica,Dolichovespula maculata, Vespa crabro, Polistes rubiginosa, Camponotusfioridanus, and Linepithema humile,crickets, grasshoppers, locusts (Orthoptera), e.g. Acheta domestica,Gryllotalpa gryllotalpa, Locusta migratoria, Melanoplus bivittatus,Melanoplus femurrubrum, Melanoplus mexicanus, Melanoplus sanguinipes,Melanoplus spretus, Nomadacris septemfasciata, Schistocerca americana,Schistocerca gregaria, Dociostaurus maroccanus, Tachycines asynamorus,Oedaleus senegalensis, Zonozerus variegatus, Hieroglyphus daganensis,Kraussaria angulifera, Calliptamus italicus, Chortoicetes terminifera,and Locustana pardalina,Arachnoidea, such as arachnids (Acarina), e.g. of the familiesArgasidae, Ixodidae and Sarcoptidae, such as Amblyomma americanum,Amblyomma variegatum, Amblyomma maculatum, Argas persicus, Boophilusannulatus, Boophilus decoloratus, Boophilus microplus, Dermacentorsilvarum, Dermacentor andersoni, Dermacentor variabilis, Hyalommatruncatum, Ixodes ricinus, Ixodes rubicundus, Ixodes scapularis, Ixodesholocyclus, Ixodes pacificus, Ornithodorus moubata, Ornithodorus hermsi,Ornithodorus turicata, Ornithonyssus bacoti, Otobius megnini,Dermanyssus gallinae, Psoroptes ovis, Rhipicephalus sanguineus,Rhipicephalus appendiculatus, Rhipicephalus evertsi, Sarcoptes scabiei,and Eriophyidae spp. such as Aculus schlechtendali, Phyllocoptrataoleivora and Eriophyes sheldoni; Tarsonemidae spp. such as Phytonemuspallidus and Polyphagotarsonemus latus; Tenuipalpidae spp. such asBrevipalpus phoenicis; Tetranychidae spp. such as Tetranychuscinnabarinus, Tetranychus kanzawai, Tetranychus pacificus, Tetranychustelarius and Tetranychus urticae, Panonychus ulmi, Panonychus citri, andOligonychus pratensis; Araneida, e.g. Latrodectus mactans, andLoxosceles reclusa,fleas (Siphonaptera), e.g. Ctenocephalides felis, Ctenocephalides canis,Xenopsylla cheopis, Pulex irritans, Tunga penetrans, and Nosopsyllusfasciatus,silverfish, firebrat (Thysanura), e.g. Lepisma saccharina and Thermobiadomestica,centipedes (Chilopoda), e.g. Scutigera coleoptrata,millipedes (Diplopoda), e.g. Narceus spp.,Earwigs (Dermaptera), e.g. forficula auricularia,lice (Phthiraptera), e.g. Pediculus humanus capitis, Pediculus humanuscorporis, Pthirus pubis, Haematopinus eurysternus, Haematopinus suis,Linognathus vituli, Bovicola bovis, Menopon gallinae, Menacanthusstramineus and Solenopotes capillatus.

Plant parasitic nematodes such as root-knot nematodes, Meloidogynearenaria, Meloidogyne chitwoodi, Meloidogyne exigua, Meloidogyne hapla,Meloidogyne incognita, Meloidogyne javanica and other Meloidogynespecies; cyst nematodes, Globodera rostochiensis, Globodera pallida,Globodera tabacum and other Globodera species, Heterodera avenae,Heterodera glycines, Heterodera schachtii, Heterodera trifolii, andother Heterodera species; seed gall nematodes, Anguina funesta, Anguinatritici and other Anguina species; stem and foliar nematodes,Aphelenchoides besseyi, Aphelenchoides fragariae, Aphelenchoidesritzemabosi and other Aphelenchoides species; sting nematodes,Belonolaimus longicaudatus and other Belonolaimus species; pinenematodes, Bursaphelenchus xylophilus and other Bursaphelenchus species;ring nematodes, Criconema species, Criconemella species, Criconemoidesspecies, and Mesocriconema species; stem and bulb nematodes, Ditylenchusdestructor, Ditylenchus dipsaci, Ditylenchus myceliophagus and otherDitylenchus species; awl nematodes, Dolichodorus species; spiralnematodes, Helicotylenchus dihystera, Helicotylenchus multicinctus andother Helicotylenchus species, Rotylenchus robustus and otherRotylenchus species; sheath nematodes, Hemicycliophora species andHemicriconemoides species; Hirshmanniella species; lance nematodes,Hoplolaimus columbus, Hoplolaimus galeatus and other Hoplolaimusspecies; false root-knot nematodes, Nacobbus aberrans and other Nacobbusspecies; needle nematodes, Longidorus elongates and other Longidorusspecies; pin nematodes, Paratylenchus species; lesion nematodes,Pratylenchus brachyurus, Pratylenchus coffeae, Pratylenchus curvitatus,Pratylenchus goodeyi, Pratylencus neglectus, Pratylenchus penetrans,Pratylenchus scribneri, Pratylenchus vulnus, Pratylenchus zeae and otherPratylenchus species; Radinaphelenchus cocophilus and otherRadinaphelenchus species; burrowing nematodes, Radopholus similis andother Radopholus species; reniform nematodes, Rotylenchulus reniformisand other Rotylenchulus species; Scutellonema species; stubby rootnematodes, Trichodorus primitivus and other Trichodorus species;Paratrichodorus minor and other Paratrichodorus species; stuntnematodes, Tylenchorhynchus claytoni, Tylenchorhynchus dubius and otherTylenchorhynchus species and Merlinius species; citrus nematodes,Tylenchulus semipenetrans and other Tylenchulus species; daggernematodes, Xiphinema americanum, Xiphinema index, Xiphinemadiversicaudatum and other Xiphinema species; and other plant parasiticnematode species.

Moreover, the inventive mixtures are especially useful for the controlof Lepidoptera, Coleoptera, Diptera, Thysanoptera and Hymenoptera.

In particular the inventive mixtures are useful for the control ofThysanoptera and Hymenoptera, especially Hymenoptera.

Formulations

The mixtures according to the present invention can be converted intothe customary formulations, for example solutions, emulsions,suspensions, dusts, powders, pastes and granules. The use form dependson the particular intended purpose; in each case, it should ensure afine and even distribution of the compounds according to the invention.

The formulations are prepared in a known manner (see e.g. for reviewU.S. Pat. No. 3,060,084, EP-A 707 445 (for liquid concentrates),Browning, “Agglomeration”, Chemical Engineering, Dec. 4, 1967, 147-48,Perry's Chemical Engineer's Handbook, 4th Ed., McGraw-Hill, New York,1963, pages 8-57 and et seq. WO 91/13546, U.S. Pat. No. 4,172,714, U.S.Pat. No. 4,144,050, U.S. Pat. No. 3,920,442, U.S. Pat. No. 5,180,587,U.S. Pat. No. 5,232,701, U.S. Pat. No. 5,208,030, GB 2,095,558, U.S.Pat. No. 3,299,566, Klingman, Weed Control as a Science, John Wiley andSons, Inc., New York, 1961, Hance et al., Weed Control Handbook, 8thEd., Blackwell Scientific Publications, Oxford, 1989 and Mollet, H.,Grubemann, A., Formulation technology, Wiley VCH Verlag GmbH, Weinheim(Germany), 2001, 2. D. A. Knowles, Chemistry and Technology ofAgrochemical Formulations, Kluwer Academic Publishers, Dordrecht, 1998(ISBN 0-7514-0443-8), for example by extending the active compound withauxiliaries suitable for the formulation of agrochemicals, such assolvents and/or carriers, if desired emulsifiers, surfactants anddispersants, preservatives, antifoaming agents, anti-freezing agents,for seed treatment formulation also optionally gelling agents.

Examples of suitable solvents are water, aromatic solvents (for exampleSolvesso products, xylene), paraffins (for example mineral oilfractions), alcohols (for example methanol, butanol, pentanol, benzylalcohol), ketones (for example cyclohexanone, gammabutyrolactone),pyrrolidones (NMP(N-methyl-pyrrolidone), NOP (N-octylpyrrolidone)),acetates (glycol diacetate), glycols, fatty acid dimethylamides, fattyacids and fatty acid esters. In principle, solvent mixtures may also beused.

Suitable emulsifiers are nonionic and anionic emulsifiers (for examplepolyoxyethylene fatty alcohol ethers, alkylsulfonates andarylsulfonates).

Examples of dispersants are lignin-sulfite waste liquors andmethylcellulose.

Suitable surfactants used are alkali metal, alkaline earth metal andammonium salts of lignosulfonic acid, naphthalenesulfonic acid,phenolsulfonic acid, dibutylnaphthalene-sulfonic acid,alkylarylsulfonates, alkyl sulfates, alkylsulfonates, fatty alcoholsulfates, fatty acids and sulfated fatty alcohol glycol ethers,furthermore condensates of sulfonated naphthalene and naphthalenederivatives with formaldehyde, condensates of naphthalene or ofnaphthalenesulfonic acid with phenol and formaldehyde, polyoxyethyleneoctylphenol ether, ethoxylated isooctylphenol, octylphenol, nonylphenol,alkylphenol polyglycol ethers, tributylphenyl polyglycol ether,tristearylphenyl polyglycol ether, alkylaryl polyether alcohols, alcoholand fatty alcohol ethylene oxide condensates, ethoxylated castor oil,polyoxyethylene alkyl ethers, ethoxylated polyoxypropyl-ene, laurylalcohol polyglycol ether acetal, sorbitol esters, lignosulfite wasteliquors and methylcellulose.

Substances which are suitable for the preparation of directly sprayablesolutions, emulsions, pastes or oil dispersions are mineral oilfractions of medium to high boiling point, such as kerosene or dieseloil, furthermore coal tar oils and oils of vegetable or animal origin,aliphatic, cyclic and aromatic hydrocarbons, for example toluene,xylene, paraffin, tetrahydronaphthalene, alkylated naphthalenes or theirderivatives, methanol, ethanol, propanol, butanol, cyclohexanol,cyclohexanone, isophorone, highly polar solvents, for example dimethylsulfoxide, N-methylpyrrolidone or water.

Also anti-freezing agents such as glycerin, ethylene glycol, propyleneglycol and bactericides such as can be added to the formulation.

Suitable antifoaming agents are for example antifoaming agents based onsilicon or magnesium stearate.

A suitable preservative is e.g. dichlorophen.

An example of a gelling agent is carrageen (Satiagel®)

Powders, materials for spreading and dustable products can be preparedby mixing or concomitantly grinding the active substances with a solidcarrier.

Granules, for example coated granules, impregnated granules andhomogeneous granules, can be prepared by binding the active compounds tosolid carriers.

Examples of solid carriers are mineral earths such as silica gels,silicates, talc, kaolin, attaclay, limestone, lime, chalk, bole, loess,clay, dolomite, diatomaceous earth, calcium sulfate, magnesium sulfate,magnesium oxide, ground synthetic materials, fertilizers, such as, forexample, ammonium sulfate, ammonium phosphate, ammonium nitrate, ureas,and products of vegetable origin, such as cereal meal, tree bark meal,wood meal and nutshell meal, cellulose powders and other solid carriers.

In general, the formulations comprise from 0.01 to 95% by weight,preferably from 0.1 to 90% by weight, of the active compounds. In thiscase, the active compounds are employed in a purity of from 90% to 100%by weight, preferably 95% to 100% by weight (according to NMR spectrum).

For seed treatment purposes, respective formulations can be diluted 2-10fold leading to concentrations in the ready to use preparations of 0.01to 60% by weight active compounds by weight, preferably 0.1 to 40% byweight.

The mixtures of the present invention can be used as such, in the formof their formulations or the use forms prepared therefrom, for examplein the form of directly sprayable solutions, powders, suspensions ordispersions, emulsions, oil dispersions, pastes, dustable products,materials for spreading, or granules, by means of spraying, atomizing,dusting, spreading or pouring. The use forms depend entirely on theintended purposes; they are intended to ensure in each case the finestpossible distribution of the active compounds according to theinvention.

Aqueous use forms can be prepared from emulsion concentrates, pastes orwettable powders (sprayable powders, oil dispersions) by adding water.To prepare emulsions, pastes or oil dispersions, the substances, as suchor dissolved in an oil or solvent, can be homogenized in water by meansof a wetter, tackifier, dispersant or emulsifier. However, it is alsopossible to prepare concentrates composed of active substance, wetter,tackifier, dispersant or emulsifier and, if appropriate, solvent or oil,and such concentrates are suitable for dilution with water.

The active compound concentrations in the ready-to-use preparations canbe varied within relatively wide ranges. In general, they are from0.0001 to 10%, preferably from 0.01 to 1% per weight.

The active compound(s) may also be used successfully in theultra-low-volume process (ULV), it being possible to apply formulationscomprising over 95% by weight of active compound, or even to apply theactive compound without additives.

The following are examples of formulations:

1. Products for dilution with water for foliar applications. For seedtreatment purposes, such products may be applied to the seed diluted orundiluted.

A) Water-Soluble Concentrates (SL, LS)

10 parts by weight of the active compound(s) are dissolved in 90 partsby weight of water or a water-soluble solvent. As an alternative,wetters or other auxiliaries are added. The active compound(s)dissolve(s) upon dilution with water, whereby a formulation with 10%(w/w) of active compound(s) is obtained.

B) Dispersible Concentrates (DC)

20 parts by weight of the active compound(s) are dissolved in 70 partsby weight of cyclohexanone with addition of 10 parts by weight of adispersant, for example polyvinylpyrrolidone. Dilution with water givesa dispersion, whereby a formulation with 20% (w/w) of active compound(s)is obtained.

C) Emulsifiable Concentrates (EC)

15 parts by weight of the active compound(s) are dissolved in 7 parts byweight of xylene with addition of calcium dodecylbenzenesulfonate andcastor oil ethoxylate (in each case 5 parts by weight). Dilution withwater gives an emulsion, whereby a formulation with 15% (w/w) of activecompound(s) is obtained.

D) Emulsions (EW, EO, ES)

25 parts by weight of the active compound(s) are dissolved in 35 partsby weight of xylene with addition of calcium dodecylbenzenesulfonate andcastor oil ethoxylate (in each case 5 parts by weight). This mixture isintroduced into 30 parts by weight of water by means of an emulsifiermachine (e.g. Ultraturrax) and made into a homogeneous emulsion.Dilution with water gives an emulsion, whereby a formulation with 25%(w/w) of active compound(s) is obtained.

E) Suspensions (SC, OD, FS)

In an agitated ball mill, 20 parts by weight of the active compound(s)are comminuted with addition of 10 parts by weight of dispersants,wetters and 70 parts by weight of water or of an organic solvent to givea fine active compound(s) suspension. Dilution with water gives a stablesuspension of the active compound(s), whereby a formulation with 20%(w/w) of active compound(s) is obtained.

F) Water-Dispersible Granules and Water-Soluble Granules (WG, SG)

50 parts by weight of the active compound(s) are ground finely withaddition of 50 parts by weight of dispersants and wetters and made aswater-dispersible or water-soluble granules by means of technicalappliances (for example extrusion, spray tower, fluidized bed). Dilutionwith water gives a stable dispersion or solution of the activecompound(s), whereby a formulation with 50% (w/w) of active compound(s)is obtained.

G) Water-Dispersible Powders and Water-Soluble Powders (WP, SP, SS, WS)

75 parts by weight of the active compound(s) are ground in arotor-stator mill with addition of 25 parts by weight of dispersants,wetters and silica gel. Dilution with water gives a stable dispersion orsolution of the active compound(s), whereby a formulation with 75% (w/w)of active compound(s) is obtained.

H) Gel-Formulation (GF)

In an agitated ball mill, 20 parts by weight of the active compound(s)are comminuted with addition of 10 parts by weight of dispersants, 1part by weight of gelling agent wetters and 70 parts by weight of wateror of an organic solvent to give a fine active compound(s) suspension.Dilution with water gives a stable suspension of the active compound(s),whereby a formulation with 20% (w/w) of active compound(s) is obtained.

2. Products to be applied undiluted for foliar applications. For seedtreatment purposes, such products may be applied to the seed diluted orundiluted.

I) Dustable Powders (DP, DS)

5 parts by weight of the active compound(s) are ground finely and mixedintimately with 95 parts by weight of finely divided kaolin. This givesa dustable product having 5% (w/w) of active compound(s).

J) Granules (GR, FG, GG, MG)

0.5 part by weight of the active compound(s) is ground finely andassociated with 95.5 parts by weight of carriers, whereby a formulationwith 0.5% (w/w) of active compound(s) is obtained. Current methods areextrusion, spray-drying or the fluidized bed. This gives granules to beapplied undiluted for foliar use.

K) ULV Solutions (UL)

10 parts by weight of the active compound(s) are dissolved in 90 partsby weight of an organic solvent, for example xylene. This gives aproduct having 10% (w/w) of active compound(s), which is appliedundiluted for foliar use.

Various types of oils, wetters, adjuvants, herbicides, fungicides, otherpesticides, or bactericides may be added to the active ingredients, ifappropriate just immediately prior to use (tank mix). These agentsusually are admixed with the agents according to the invention in aweight ratio of 1:10 to 10:1.

Applications

The compounds I and the one or more compound(s) II can be appliedsimultaneously, that is jointly or separately, or in succession, thesequence, in the case of separate application, generally not having anyeffect on the result of the control measures.

The mixtures of the invention are employed as such or in form ofcompositions by treating the insects or the plants, plant propagationmaterials, such as seeds, soil, surfaces, materials or rooms to beprotected from insecticidal attack with a insecticidally effectiveamount of the active compounds. The application can be carried out bothbefore and after the infection of the plants, plant propagationmaterials, such as seeds, soil, surfaces, materials or rooms by theinsects.

The compounds I and the one or more compound(s) II are usually appliedin a weight ratio of from 500:1 to 1:100, preferably from 20:1 to 1:50,in particular from 5:1 to 1:20.

Depending on the desired effect, the application rates of the mixturesaccording to the invention are from 5 g/ha to 2000 g/ha, preferably from50 to 1500 g/ha, in particular from 50 to 750 g/ha.

The mixtures according to the invention are effective through bothcontact and ingestion.

According to a preferred embodiment of the invention, the mixturesaccording to the present invention are employed via soil application.Soil application is especially favorable for use against ants, termites,crickets, or cockroaches.

According to another preferred embodiment of the invention, for useagainst non crop pests such as ants, termites, wasps, flies, mosquitoes,crickets, locusts, or cockroaches the mixtures according to the presentinvention are prepared into a bait preparation.

The bait can be a liquid, a solid or a semisolid preparation (e.g. agel).

Another aspect of the present invention is when preparing the mixtures,it is preferred to employ the pure active compounds I and II, to whichfurther active compounds, e.g. against harmful fungi or havingherbicidal activity, or growth-regulating agents or fertilizers can beadded.

Compositions of this invention may further contain other activeingredients than those listed above. For example fungicides, herbicides,fertilizers such as ammonium nitrate, urea, potash, and superphosphate,phytotoxicants and plant growth regulators and safeners. Theseadditional ingredients may be used sequentially or in combination withthe above-described compositions, if appropriate also added onlyimmediately prior to use (tank mix). For example, the plant(s) may besprayed with a composition of this invention either before or afterbeing treated with other active ingredients.

The mixtures according to the invention can be applied to any and alldevelopmental stages, such as egg, larva, pupa, and adult. The pests maybe controlled by contacting the target pest, its food supply, habitat,breeding ground or its locus with a pesticidally effective amount of theinventive mixtures or of compositions comprising the mixtures. “Locus”means a plant, seed, soil, area, material or environment in which a pestis growing or may grow.

In general, “pesticidally effective amount” means the amount of theinventive mixtures or of compositions comprising the mixtures needed toachieve an observable effect on growth, including the effects ofnecrosis, death, retardation, prevention, and removal, destruction, orotherwise diminishing the occurrence and activity of the targetorganism. The pesticidally effective amount can vary for the variousmixtures and/or compositions used in the invention. A pesticidallyeffective amount of the mixtures and/or compositions will also varyaccording to the prevailing conditions such as desired pesticidal effectand duration, weather, target species, locus, mode of application, andthe like.

The inventive mixtures or compositions of these mixtures can also beemployed for protecting plants from attack or infestation by insects,acarids or nematodes comprising contacting a plant, or soil or water inwhich the plant is growing.

The inventive mixtures are effective through both contact (via soil,glass, wall, bed net, carpet, plant parts or animal parts), andingestion (bait, or plant part) and through trophallaxis and transfer.

Preferred application methods are into water bodies, via soil, cracksand crevices, pastures, manure piles, sewers, into water, on floor,wall, or by perimeter spray application and bait.

According to another preferred embodiment of the invention, for useagainst non crop pests such as ants, termites, wasps, flies, mosquitoes,crickets, locusts, or cockroaches the inventive mixtures are preparedinto a bait preparation.

The bait can be a liquid, a solid or a semisolid preparation (e.g. agel). The bait employed in the composition is a product which issufficiently attractive to incite insects such as ants, termites, wasps,flies, mosquitoes, crickets etc. or cockroaches to eat it.

This attractant may be chosen from feeding stimulants or para and/or sexpheromones readily known in the art.

Methods to control infectious diseases transmitted by insects (e.g.malaria, dengue and yellow fever, lymphatic filariasis, andleishmaniasis) with the inventive mixtures and their respectivecompositions also comprise treating surfaces of huts and houses, airspraying and impregnation of curtains, tents, clothing items, bed nets,tsetse-fly trap or the like. Insecticidal compositions for applicationto fibers, fabric, knitgoods, nonwovens, netting material or foils andtarpaulins preferably comprise a composition including the inventivemixtures, optionally a repellent and at least one binder.

The inventive mixtures and the compositions comprising them can be usedfor protecting wooden materials such as trees, board fences, sleepers,etc. and buildings such as houses, outhouses, factories, but alsoconstruction materials, furniture, leathers, fibers, vinyl articles,electric wires and cables etc. from ants and/or termites, and forcontrolling ants and termites from doing harm to crops or human being(e.g. when the pests invade into houses and public facilities).

In the case of soil treatment or of application to the pests dwellingplace or nest, the quantity of active ingredient(s) ranges from 0.0001to 500 g per 100 m², preferably from 0.001 to 20 g per 100 m².

Customary application rates in the protection of materials are, forexample, from 0.01 g to 1000 g of active compound(s) per m² treatedmaterial, desirably from 0.1 g to 50 g per m².

Insecticidal compositions for use in the impregnation of materialstypically contain from 0.001 to 95 weight %, preferably from 0.1 to 45weight %, and more preferably from 1 to 25 weight % of at least onerepellent and/or insecticide.

For use in bait compositions, the typical content of activeingredient(s) is from 0.0001 weight % to 15 weight %, desirably from0.001 weight % to 5% weight % of active compound. The composition usedmay also comprise other additives such as a solvent of the activematerial, a flavoring agent, a preserving agent, a dye or a bitteragent. Its attractiveness may also be enhanced by a special color, shapeor texture.

For use in spray compositions, the content of the mixture of the activeingredients is from 0.001 to 80 weights %, preferably from 0.01 to 50weight % and most preferably from 0.01 to 15 weight %.

For use in treating crop plants, the rate of application of the mixtureof the active ingredients of this invention may be in the range of 0.1 gto 4000 g per hectare, desirably from 25 g to 600 g per hectare, moredesirably from 50 g to 500 g per hectare.

In the context of the present invention, the term plant refers to anentire plant, a part of the plant or the plant propagation material.

The mixtures of the present invention and the compositions comprisingthem are particularly important in the control of a multitude of insectson various cultivated plants.

Plants which can be treated with the inventive mixtures include allgenetically modified plants or transgenic plants, e.g. crops whichtolerate the action of herbicides or fungicides or insecticides owing tobreeding, including genetic engineering methods, or plants which havemodified characteristics in comparison with existing plants, which canbe generated for example by traditional breeding methods and/or thegeneration of mutants, or by recombinant procedures.

The term “plant propagation material” is to be understood to denote allthe generative parts of the plant such as seeds and vegetative plantmaterial such as cuttings and tubers (e. g. potatoes), which can be usedfor the multiplication of the plant. This includes seeds, roots, fruits,tubers, bulbs, rhizomes, shoots, sprouts and other parts of plants.Seedlings and young plants, which are to be transplanted aftergermination or after emergence from soil, may also be mentioned. Theseyoung plants may also be protected before transplantation by a total orpartial treatment by immersion or pouring.

The term “cultivated plants” is to be understood as including plantswhich have been modified by breeding, mutagenesis or geneticengineering. Genetically modified plants are plants, which geneticmaterial has been so modified by the use of recombinant DNA techniquesthat under natural circumstances cannot be obtained by cross breeding,mutations or natural recombination. Typically, one or more genes havebeen integrated into the genetic material of a genetically modifiedplant in order to improve certain properties of the plant.

The term “cultivated plants” is to be understood also including plantsthat have been rendered tolerant to applications of specific classes ofherbicides, such as hydroxy-phenylpyruvate dioxygenase (HPPD)inhibitors; acetolactate synthase (ALS) inhibitors, such as sulfonylureas (see e. g. U.S. Pat. No. 6,222,100, WO 01/82685, WO 00/26390, WO97/41218, WO 98/02526, WO 98/02527, WO 04/106529, WO 05/20673, WO03/14357, WO 03/13225, WO 03/14356, WO 04/16073) or imidazolinones (seee. g. U.S. Pat. No. 6,222,100, WO 01/82685, WO 00/26390, WO 97/41218, WO98/02526, WO 98/02527, WO 04/106529, WO 05/20673, WO 03/14357, WO03/13225, WO 03/14356, WO 04/16073); enolpyruvylshikimate-3-phosphatesynthase (EPSPS) inhibitors, such as glyphosate (see e. g. WO 92/00377);glutamine synthetase (GS) inhibitors, such as glufosinate (see e. g.EP-A-0242236, EP-A-242246) or oxynil herbicides (see e. g. U.S. Pat. No.5,559,024) as a result of conventional methods of breeding or geneticengineering. Several cultivated plants have been rendered tolerant toherbicides by conventional methods of breeding (mutagenesis), forexample Clearfield® summer rape (Canola) being tolerant toimidazolinones, e. g. imazamox. Genetic engineering methods have beenused to render cultivated plants, such as soybean, cotton, corn, beetsand rape, tolerant to herbicides, such as glyphosate and glufosinate,some of which are commercially available under the trade namesRoundupReady® (glyphosate) and LibertyLink® (glufosinate).

The term “cultivated plants” is to be understood also including plantsthat are by the use of recombinant DNA techniques capable to synthesizeone or more insecticidal proteins, especially those known from thebacterial genus Bacillus, particularly from Bacillus thuringiensis, suchas ä-endotoxins, e. g. CryIA(b), CryIA(c), CryIF, CryIF(a2), CryIIA(b),CryIIIA, CryIIIB(b1) or Cry9c; vegetative insecticidal proteins (VIP),e. g. VIP 1, VIP2, VIP3 or VIP3A; insecticidal proteins of bacteriacolonizing nematodes, for example Photorhabdus spp. or Xenorhabdus spp.;toxins produced by animals, such as scorpion toxins, arachnid toxins,wasp toxins, or other insect-specific neurotoxins; toxins produced byfungi, such Streptomycetes toxins, plant lectins, such as pea or barleylectins; agglutinins; proteinase inhibitors, such as trypsin inhibitors,serine protease inhibitors, patatin, cystatin or papain inhibitors;ribosome-inactivating proteins (RIP), such as ricin, maize-RIP, abrin,luffin, saporin or bryodin; steroid metabolism enzymes, such as3-hydroxysteroid oxidase, ecdysteroid-IDP-glycosyl-transferase,cholesterol oxidases, ecdysone inhibitors or HMG-CoA-reductase; ionchannel blockers, such as blockers of sodium or calcium channels;juvenile hormone esterase; diuretic hormone receptors (helicokininreceptors); stilben synthase, bibenzyl synthase, chitinases orglucanases. In the context of the present invention these insecticidalproteins or toxins are to be understood expressly also as pre-toxins,hybrid proteins, truncated or otherwise modified proteins. Hybridproteins are characterized by a new combination of protein domains,(see, for example WO 02/015701). Further examples of such toxins orgenetically-modified plants capable of synthesizing such toxins aredis-closed, for example, in EP-A 374 753, WO 93/007278, WO 95/34656,EP-A 427 529, EP-A 451 878, WO 03/018810 and WO 03/052073. The methodsfor producing such genetically modified plants are generally known tothe person skilled in the art and are described, for example, in thepublications mentioned above. These insecticidal proteins contained inthe genetically modified plants impart to the plants producing theseproteins tolerance to harmful pests from all taxonomic groups ofinsects, especially to beetles (Coeloptera), two-winged insects(Diptera), and butterflies (Lepidoptera).

The term “cultivated plants” is to be understood also including plantsthat are by the use of recombinant DNA techniques capable to synthesizeone or more proteins to in-crease the resistance or tolerance of thoseplants to bacterial, viral or fungal pathogens. Examples of suchproteins are the so-called “pathogenesis-related proteins” (PR proteins,see, for example EP-A 0 392 225), plant disease resistance genes (forexample potato cultivars, which express resistance genes acting againstPhytophthora infestans derived from the mexican wild potato Solanumbulbocastanum) or T4-lyso-zym (e. g. potato cultivars capable ofsynthesizing these proteins with increased resistance against bacteriasuch as Erwinia amylvora). The methods for producing such geneticallymodified plants are generally known to the person skilled in the art andare described, for example, in the publications mentioned above.

The term “cultivated plants” is to be understood also including plantsthat are by the use of recombinant DNA techniques capable to synthesizeone or more proteins to increase the productivity (e. g. bio massproduction, grain yield, starch content, oil content or proteincontent), tolerance to drought, salinity or other growth-limitingenviron-mental factors or tolerance to pests and fungal, bacterial orviral pathogens of those plants.

The term “cultivated plants” is to be understood also including plantsthat contain by the use of recombinant DNA techniques a modified amountof substances of content or new substances of content, specifically toimprove human or animal nutrition, for ex-ample oil crops that producehealth-promoting long-chain omega-3 fatty acids or unsaturated omega-9fatty acids (e. g. Nexera° rape).

The term “cultivated plants” is to be understood also including plantsthat contain by the use of recombinant DNA techniques a modified amountof substances of content or new substances of content, specifically toimprove raw material production, for example potatoes that produceincreased amounts of amylopectin (e. g. Amflora° potato).

Some of the inventive mixtures have systemic action and can therefore beused for the protection of the plant shoot against foliar pests as wellas for the treatment of the seed and roots against soil pests.

Seed Treatment

The mixtures according to the present invention are therfore suitablefor the treatment of seeds in order to protect the seed from insectpest, in particular from soil-living insect pests and the resultingplant's roots and shoots against soil pests and foliar insects. Theprotection of the resulting plant's roots and shoots is preferred.

More preferred is the protection of resulting plant's shoots frompiercing and sucking insects.

The present invention therefore comprises a method for the protection ofseeds from insects, in particular from soil insects and of theseedlings' roots and shoots from insects, in particular from soil andfoliar insects, said method comprising contacting the seeds beforesowing and/or after pregermination with mixtures according to thepresent invention. Particularly preferred is a method, wherein theplant's roots and shoots are protected, more preferably a method,wherein the plants shoots are protected form piercing and suckinginsects, most preferably a method, wherein the plants shoots areprotected from aphids.

The term seed embraces seeds and plant propagules of all kinds includingbut not limited to true seeds, seed pieces, suckers, corms, bulbs,fruit, tubers, grains, cuttings, cut shoots and the like and means in apreferred embodiment true seeds.

The term seed treatment comprises all suitable seed treatment techniquesknown in the art, such as seed dressing, seed coating, seed dusting,seed soaking and seed pelleting.

The present invention also comprises seeds coated with or containing theactive compound(s). The term “coated with and/or containing” generallysignifies that the active ingredient(s) are for the most part on thesurface of the propagation product at the time of application, althougha greater or lesser part of the ingredient may penetrate into thepropagation product, depending on the method of application. When thesaid propagation product are (re)planted, it may absorb the activeingredient.

Suitable seeds are seeds of cereals, root crops, oil crops, vegetables,spices, ornamentals, for example seed of durum and other wheat, barley,oats, rye, maize (fodder maize and sugar maize/sweet and field corn),soybeans, oil crops, crucifers, cotton, sunflowers, bananas, rice,oilseed rape, turnip rape, sugarbeet, fodder beet, eggplants, potatoes,grass, lawn, turf, fodder grass, tomatoes, leeks, pumpkin/squash,cabbage, iceberg lettuce, pepper, cucumbers, melons, Brassica species,melons, beans, peas, garlic, onions, carrots, tuberous plants such aspotatoes, sugar cane, tobacco, grapes, petunias, geranium/pelargoniums,pansies and impatiens.

In addition, the mixtures according to the invention may also be usedfor the treatment seeds from plants, which tolerate the action ofherbicides or fungicides or insecticides owing to breeding, includinggenetic engineering methods.

For example, the active mixtures can be employed in treatment of seedsfrom plants, which are resistant to herbicides from the group consistingof the sulfonylureas, imidazolinones, glufosinate-ammonium orglyphosate-isopropylammonium and analogous active substances (see forexample, EP-A-0242236, EP-A-242246) (WO 92/00377) (EP-A-0257993, U.S.Pat. No. 5,013,659) or in transgenic crop plants, for example cotton,with the capability of producing Bacillus thuringiensis toxins (Bttoxins) which make the plants resistant to certain pests (EP-A-0142924,EP-A-0193259),

Furthermore, the mixtures according to the present invention can be usedalso for the treatment of seeds from plants, which have modifiedcharacteristics in comparison with existing plants consist, which can begenerated for example by traditional breeding methods and/or thegeneration of mutants, or by recombinant procedures). For example, anumber of cases have been described of recombinant modifications of cropplants for the purpose of modifying the starch synthesized in the plants(e.g. WO 92/11376, WO 92/14827, WO 91/19806) or of transgenic cropplants having a modified fatty acid composition (WO 91/13972).

The seed treatment application of the mixtures is carried out byspraying or by dusting the seeds before sowing of the plants and beforeemergence of the plants.

In the treatment of seeds the corresponding formulations are applied bytreating the seeds with an effective amount of the mixture according tothe present invention. Herein, the application rates of the activecompound(s) are generally from 0.1 g to 10 kg per 100 kg of seed,preferably from 1 g to 5 kg per 100 kg of seed, in particular from 1 gto 2.5 kg per 100 kg of seed. For specific crops such as lettuce therate can be higher.

Compositions, which are especially useful for seed treatment are e.g.:

-   A Soluble concentrates (SL, LS)-   D Emulsions (EW, EO, ES)-   E Suspensions (SC, OD, FS)-   F Water-dispersible granules and water-soluble granules (WG, SG)-   G Water-dispersible powders and water-soluble powders (WP, SP, WS)-   H Gel-Formulations (GF)-   I Dustable powders (DP, DS)

Conventional seed treatment formulations include for example flowableconcentrates FS, solutions LS, powders for dry treatment DS, waterdispersible powders for slurry treatment WS, water-soluble powders SSand emulsion ES and EC and gel formulation GF. These formulations can beapplied to the seed diluted or undiluted. Application to the seeds iscarried out before sowing, either directly on the seeds or after havingpregerminated the latter

In a preferred embodiment a FS formulation is used for seed treatment.Typically, a FS formulation may comprise 1-800 g/l of activeingredient(s), 1-200 g/l Surfactant, 0 to 200 g/l antifreezing agent, 0to 400 g/l of binder, 0 to 200 g/l of a pigment and up to 1 liter of asolvent, preferably water.

Preferred FS formulations of compounds of formula I for seed treatmentusually comprise from 0.1 to 80% by weight (1 to 800 g/l) of the activeingredient(s), from 0.1 to 20% by weight (1 to 200 g/l) of at least onesurfactant, e.g. 0.05 to 5% by weight of a wetter and from 0.5 to 15% byweight of a dispersing agent, up to 20% by weight, e.g. from 5 to 20% ofan anti-freeze agent, from 0 to 15% by weight, e.g. 1 to 15% by weightof a pigment and/or a dye, from 0 to 40% by weight, e.g. 1 to 40% byweight of a binder (sticker/adhesion agent), optionally up to 5% byweight, e.g. from 0.1 to 5% by weight of a thickener, optionally from0.1 to 2% of an anti-foam agent, and optionally a preservative such as abiocide, antioxidant or the like, e.g. in an amount from 0.01 to 1% byweight and a filler/vehicle up to 100% by weight.

Seed Treatment formulations may additionally also comprise binders andoptionally colorants.

Binders can be added to improve the adhesion of the active materials onthe seeds after treatment. Suitable binders are block copolymers EO/POsurfactants but also polyvinylalcoholsl, polyvinylpyrrolidones,polyacrylates, polymethacrylates, polybutenes, polyisobutylenes,polystyrene, polyethyleneamines, polyethyleneamides, polyethyleneimines(Lupasol®, Polymin®), polyethers, polyurethans, polyvinylacetate, tyloseand copolymers derived from these polymers.

Optionally, also colorants can be included in the formulation. Suitablecolorants or dyes for seed treatment formulations are Rhodamin B, C.I.Pigment Red 112, C.I. Solvent Red 1, pigment blue 15:4, pigment blue15:3, pigment blue 15:2, pigment blue 15:1, pigment blue 80, pigmentyellow 1, pigment yellow 13, pigment red 112, pigment red 48:2, pigmentred 48:1, pigment red 57:1, pigment red 53:1, pigment orange 43, pigmentorange 34, pigment orange 5, pigment green 36, pigment green 7, pigmentwhite 6, pigment brown 25, basic violet 10, basic violet 49, acid red51, acid red 52, acid red 14, acid blue 9, acid yellow 23, basic red 10,basic red 108.

The invention also relates to seed comprising mixtures according to thepresent invention. The amount of the compound I or the agriculturallyuseful salt thereof will in general vary from 0.1 g to 10 kg per 100 kgof seed, preferably from 1 g to 5 kg per 100 kg of seed, in particularfrom 1 g to 1000 g per 100 kg of seed.

Animal Health

The mixtures of the present invention are in particular also suitablefor being used for combating parasites in and on animals.

An object of the present invention is therefore also to provide newmethods to control parasites in and on animals. Another object of theinvention is to provide safer pesticides for animals. Another object ofthe invention is further to provide pesticides for animals that may beused in lower doses than existing pesticides. And another object of theinvention is to provide pesticides for animals, which provide a longresidual control of the parasites.

The invention also relates to compositions containing a parasiticidallyeffective amount of compounds of formula I or the enantiomers orveterinarily acceptable salts thereof and an acceptable carrier, forcombating parasites in and on animals.

The present invention also provides a method for treating, controlling,preventing and protecting animals against infestation and infection byparasites, which comprises orally, topically or parenterallyadministering or applying to the animals a parasiticidally effectiveamount of mixture of the present invention or a composition comprisingit.

The invention also provides a process for the preparation of acomposition for treating, controlling, preventing or protecting animalsagainst infestation or infection by parasites which comprises aparasiticidally effective amount of a mixture of the present inventionor a composition comprising it.

Activity of compounds against agricultural pests does not suggest theirsuitability for control of endo- and ectoparasites in and on animalswhich requires, for example, low, non-emetic dosages in the case of oralapplication, metabolic compatibility with the animal, low toxicity, anda safe handling.

Surprisingly it has now been found that mixtures of the presentinvention are suitable for combating endo- and ectoparasites in and onanimals.

Mixtures of the present invention and compositions comprising them arepreferably used for controlling and preventing infestations andinfections animals including warm-blooded animals (including humans) andfish. They are for example suitable for controlling and preventinginfestations and infections in mammals such as cattle, sheep, swine,camels, deer, horses, pigs, poultry, rabbits, goats, dogs and cats,water buffalo, donkeys, fallow deer and reindeer, and also infur-bearing animals such as mink, chinchilla and raccoon, birds such ashens, geese, turkeys and ducks and fish such as fresh- and salt-waterfish such as trout, carp and eels.

Mixtures of the present invention and compositions comprising them arepreferably used for controlling and preventing infestations andinfections in domestic animals, such as dogs or cats.

Infestations in warm-blooded animals and fish include, but are notlimited to, lice, biting lice, ticks, nasal bots, keds, biting flies,muscoid flies, flies, myiasitic fly larvae, chiggers, gnats, mosquitoesand fleas.

The mixtures of the present invention and compositions comprising themare suitable for systemic and/or non-systemic control of ecto- and/orendoparasites. They are active against all or some stages ofdevelopment.

The mixtures of the present invention are especially useful forcombating ectoparasites.

The mixture of the present invention are especially useful for combatingparasites of the following orders and species, respectively:

fleas (Siphonaptera), e.g. Ctenocephalides felis, Ctenocephalides canis,Xenopsylla cheopis, Pulex irritans, Tunga penetrans, and Nosopsyllusfasciatus,cockroaches (Blattaria-Blattodea), e.g. Blattella germanica, Blattellaasahinae, Periplaneta americana, Periplaneta japonica, Periplanetabrunnea, Periplaneta fuligginosa, Periplaneta australasiae, and Blattaorientalis,flies, mosquitoes (Diptera), e.g. Aedes aegypti, Aedes albopictus, Aedesvexans, Anastrepha ludens, Anopheles maculipennis, Anopheles crucians,Anopheles albimanus, Anopheles gambiae, Anopheles freeborni, Anophelesleucosphyrus, Anopheles minimus, Anopheles quadrimaculatus, Calliphoravicina, Chrysomya bezziana, Chrysomya hominivorax, Chrysomya macellaria,Chrysops discalis, Chrysops silacea, Chrysops atlanticus, Cochliomyiahominivorax, Cordylobia anthropophaga, Culicoides furens, Culex pipiens,Culex nigripalpus, Culex quinquefasciatus, Culex tarsalis, Culisetainornata, Culiseta melanura, Dermatobia hominis, Fannia canicularis,Gasterophilus intestinalis, Glossina morsitans, Glossina palpalis,Glossina fuscipes, Glossina tachinoides, Haematobia irritans,Haplodiplosis equestris, Hippelates spp., Hypoderma lineata, Leptoconopstorrens, Lucilia caprina, Lucilia cuprina, Lucilia sericata, Lycoriapectoralis, Mansonia spp., Musca domestica, Muscina stabulans, Oestrusovis, Phlebotomus argentipes, Psorophora columbiae, Psorophora discolor,Prosimulium mixtum, Sarcophaga haemorrhoidalis, Sarcophaga sp., Simuliumvittatum, Stomoxys calcitrans, Tabanus bovinus, Tabanus atratus, Tabanuslineola, and Tabanus similis,lice (Phthiraptera), e.g. Pediculus humanus capitis, Pediculus humanuscorporis, Pthirus pubis, Haematopinus eurysternus, Haematopinus suis,Linognathus vituli, Bovicola bovis, Menopon gallinae, Menacanthusstramineus and Solenopotes capillatus.ticks and parasitic mites (Parasitiformes): ticks (Ixodida), e.g. Ixodesscapularis, Ixodes holocyclus, Ixodes pacificus, Rhiphicephalussanguineus, Dermacentor andersoni, Dermacentor variabilis, Amblyommaamericanum, Amblyomma maculatum, Ornithodorus hermsi, Ornithodorusturicata and parasitic mites (Mesostigmata), e.g. Ornithonyssus bacotiand Dermanyssus gallinae,Actinedida (Prostigmata) and Acaridida (Astigmata) e.g. Acarapis spp.,Cheyletiella spp., Ornithocheyletia spp., Myobia spp., Psorergates spp.,Demodex spp., Trombicula spp., Listrophorus spp., Acarus spp.,Tyrophagus spp., Caloglyphus spp., Hypodectes spp., Pterolichus spp.,Psoroptes spp., Chorioptes spp., Otodectes spp., Sarcoptes spp.,Notoedres spp., Knemidocoptes spp., Cytodites spp., and Laminosioptesspp,Bugs (Heteropterida): Cimex lectularius, Cimex hemipterus, Reduviussenilis, Triatoma spp., Rhodnius ssp., Panstrongylus ssp. and Ariluscritatus,Anoplurida, e.g. Haematopinus spp., Linognathus spp., Pediculus spp.,Phtirus spp., and Solenopotes spp,Mallophagida (suborders Arnblycerina and Ischnocerina), e.g. Trimenoponspp., Menopon spp., Trinoton spp., Bovicola spp., Werneckiella spp.,Lepikentron spp., Trichodectes spp., and Felicola spp,

Roundworms Nematoda:

Wipeworms and Trichinosis (Trichosyringida), e.g. Trichinellidae(Trichinella spp.), (Trichuridae) Trichuris spp., Capillaria spp,Rhabditida, e.g. Rhabditis spp, Strongyloides spp., Helicephalobus spp,Strongylida, e.g. Strongylus spp., Ancylostoma spp., Necator americanus,Bunostomum spp. (Hookworm), Trichostrongylus spp., Haemonchuscontortus., Ostertagia spp., Cooperia spp., Nematodirus spp.,Dictyocaulus spp., Cyathostoma spp., Oesophagostomum spp., Stephanurusdentatus, Ollulanus spp., Chabertia spp., Stephanurus dentatus, Syngamustrachea, Ancylostoma spp., Uncinaria spp., Globocephalus spp., Necatorspp., Metastrongylus spp., Muellerius capillaris, Protostrongylus spp.,Angiostrongylus spp., Parelaphostrongylus spp. Aleurostrongylusabstrusus, and Dioctophyma renale,Intestinal roundworms (Ascaridida), e.g. Ascaris lumbricoides, Ascarissuum, Ascaridia galli, Parascaris equorum, Enterobius vermicularis(Threadworm), Toxocara canis, Toxascaris leonine, Skrjabinema spp., andOxyuris equi,Camallanida, e.g. Dracunculus medinensis (guinea worm)Spirurida, e.g. Thelazia spp. Wuchereria spp., Brugia spp., Onchocercaspp., Dirofilari spp.a, Dipetalonema spp., Setaria spp., Elaeophoraspp., Spirocerca lupi, and Habronema spp.,Thorny headed worms (Acanthocephala), e.g. Acanthocephalus spp.,Macracanthorhynchus hirudinaceus and Oncicola spp,

Planarians (Plathelminthes):

Flukes (Trematoda), e.g. Faciola spp., Fascioloides magna, Paragonimusspp., Dicrocoelium spp., Fasciolopsis buski, Clonorchis sinensis,Schistosoma spp., Trichobilharzia spp., Alaria alata, Paragonimus spp.,and Nanocyetes spp,

Cercomeromorpha, in particular Cestoda (Tapeworms), e.g.Diphyllobothrium spp., Tenia spp., Echinococcus spp., Dipylidiumcaninum, Multiceps spp., Hymenolepis spp., Mesocestoides spp.,Vampirolepis spp., Moniezia spp., Anoplocephala spp., Sirometra spp.,Anoplocephala spp., and Hymenolepis spp.

The mixtures of the present invention and compositions containing themare particularly useful for the control of pests from the ordersDiptera, Siphonaptera and Ixodida.

Moreover, the use of mixtures of the present invention and compositionscontaining them for combating mosquitoes is especially preferred.

The use of mixtures of the present invention and compositions containingthem for combating flies is a further preferred embodiment of thepresent invention.

Furthermore, the use of the mixtures of the present invention andcompositions containing them for combating fleas is especiallypreferred.

The use of the mixtures of the present invention and compositionscontaining them for combating ticks is a further preferred embodiment ofthe present invention.

The mixtures of the present invention also are especially useful forcombating endoparasites (roundworms nematoda, thorny headed worms andplanarians).

Administration can be carried out both prophylactically andtherapeutically.

Administration of the active compounds is carried out directly or in theform of suitable preparations, orally, topically/dermally orparenterally.

For oral administration to warm-blooded animals, the mixtures of thepresent invention may be formulated as animal feeds, animal feedpremixes, animal feed concentrates, pills, solutions, pastes,suspensions, drenches, gels, tablets, boluses and capsules. In addition,the mixtures of the present invention may be administered to the animalsin their drinking water. For oral administration, the dosage form chosenshould provide the animal with 0.01 mg/kg to 100 mg/kg of animal bodyweight per day of the formula I compound, preferably with 0.5 mg/kg to100 mg/kg of animal body weight per day.

Alternatively, the mixtures of the present invention may be administeredto animals parenterally, for example, by intraruminal, intramuscular,intravenous or subcutaneous injection. The formula I compounds may bedispersed or dissolved in a physiologically acceptable carrier forsubcutaneous injection. Alternatively, the mixtures of the presentinvention may be formulated into an implant for subcutaneousadministration. In addition the formula I compound may be transdermallyadministered to animals. For parenteral administration, the dosage formchosen should provide the animal with 0.01 mg/kg to 100 mg/kg of animalbody weight per day of the active compounds.

The mixtures of the present invention may also be applied topically tothe animals in the form of dips, dusts, powders, collars, medallions,sprays, shampoos, spot-on and pour-on formulations and in ointments oroil-in-water or water-in-oil emulsions. For topical application, dipsand sprays usually contain 0.5 ppm to 5,000 ppm and preferably 1 ppm to3,000 ppm of the active compounds. In addition, the active compoundmixtures may be formulated as ear tags for animals, particularlyquadrupeds such as cattle and sheep.

Suitable preparations are:

-   -   Solutions such as oral solutions, concentrates for oral        administration after dilution, solutions for use on the skin or        in body cavities, pouring-on formulations, gels;    -   Emulsions and suspensions for oral or dermal administration;        semi-solid preparations;    -   Formulations in which the active compound is processed in an        ointment base or in an oil-in-water or water-in-oil emulsion        base;    -   Solid preparations such as powders, premixes or concentrates,        granules, pellets, tablets, boluses, capsules; aerosols and        inhalants, and active compound-containing shaped articles.

Compositions suitable for injection are prepared by dissolving theactive ingredient in a suitable solvent and optionally adding furtheringredients such as acids, bases, buffer salts, preservatives, andsolubilizers. The solutions are filtered and filled sterile.

Suitable solvents are physiologically tolerable solvents such as water,alkanols such as ethanol, butanol, benzyl alcohol, glycerol, propyleneglycol, polyethylene glycols, N-methyl-pyrrolidone, 2-pyrrolidone, andmixtures thereof.

The active compounds can optionally be dissolved in physiologicallytolerable vegetable or synthetic oils which are suitable for injection.

Suitable solubilizers are solvents which promote the dissolution of theactive compound in the main solvent or prevent its precipitation.Examples are polyvinylpyrrolidone, polyvinyl alcohol, polyoxyethylatedcastor oil, and polyoxyethylated sorbitan ester.

Suitable preservatives are benzyl alcohol, trichlorobutanol,p-hydroxybenzoic acid esters, and n-butanol.

Oral solutions are administered directly. Concentrates are administeredorally after prior dilution to the use concentration. Oral solutions andconcentrates are prepared according to the state of the art and asdescribed above for injection solutions, sterile procedures not beingnecessary.

Solutions for use on the skin are trickled on, spread on, rubbed in,sprinkled on or sprayed on.

Solutions for use on the skin are prepared according to the state of theart and according to what is described above for injection solutions,sterile procedures not being necessary.

Further suitable solvents are polypropylene glycol, phenyl ethanol,phenoxy ethanol, ester such as ethyl or butyl acetate, benzyl benzoate,ethers such as alkyleneglycol alkylether, e.g. dipropylenglycolmonomethylether, ketons such as acetone, methylethylketone, aromatichydrocarbons, vegetable and synthetic oils, dimethylformamide,dimethylacetamide, transcutol, solketal, propylencarbonate, and mixturesthereof

It may be advantageous to add thickeners during preparation. Suitablethickeners are inorganic thickeners such as bentonites, colloidalsilicic acid, aluminium monostearate, organic thickeners such ascellulose derivatives, polyvinyl alcohols and their copolymers,acrylates and methacrylates.

Gels are applied to or spread on the skin or introduced into bodycavities. Gels are prepared by treating solutions which have beenprepared as described in the case of the injection solutions withsufficient thickener that a clear material having an ointment-likeconsistency results. The thickeners employed are the thickeners givenabove.

Pour-on formulations are poured or sprayed onto limited areas of theskin, the active compound penetrating the skin and acting systemically.

Pour-on formulations are prepared by dissolving, suspending oremulsifying the active compound in suitable skin-compatible solvents orsolvent mixtures. If appropriate, other auxiliaries such as colorants,bioabsorption-promoting substances, antioxidants, light stabilizers,adhesives are added.

Suitable solvents which are: water, alkanols, glycols, polyethyleneglycols, polypropylene glycols, glycerol, aromatic alcohols such asbenzyl alcohol, phenylethanol, phenoxyethanol, esters such as ethylacetate, butyl acetate, benzyl benzoate, ethers such as alkylene glycolalkyl ethers such as dipropylene glycol monomethyl ether, diethyleneglycol mono-butyl ether, ketones such as acetone, methyl ethyl ketone,cyclic carbonates such as propylene carbonate, ethylene carbonate,aromatic and/or aliphatic hydrocarbons, vegetable or synthetic oils,DMF, dimethylacetamide, n-alkylpyrrolidones such as methylpyrrolidone,n-butylpyrrolidone or n-octylpyrrolidone, N-methylpyrrolidone,2-pyrrolidone, 2,2-dimethyl-4-oxy-methylene-1,3-diox-olane and glycerolformal.

Suitable colorants are all colorants permitted for use on animals andwhich can be dissolved or suspended.

Suitable absorption-promoting substances are, for example, DMSO,spreading oils such as isopropyl myristate, dipropylene glycolpelargonate, silicone oils and copolymers thereof with polyethers, fattyacid esters, triglycerides, fatty alcohols.

Suitable antioxidants are sulfites or metabisulfites such as potassiummetabisulfite, ascorbic acid, butylhydroxytoluene, butylhydroxyanisole,tocopherol.

Suitable light stabilizers are, for example, novantisolic acid.

Suitable adhesives are, for example, cellulose derivatives, starchderivatives, polyacrylates, natural polymers such as alginates, gelatin.

Emulsions can be administered orally, dermally or as injections.

Emulsions are either of the water-in-oil type or of the oil-in-watertype.

They are prepared by dissolving the active compound either in thehydrophobic or in the hydrophilic phase and homogenizing this with thesolvent of the other phase with the aid of suitable emulsifiers and, ifappropriate, other auxiliaries such as colorants, absorption-promotingsubstances, preservatives, antioxidants, light stabilizers,viscosity-enhancing substances.

Suitable hydrophobic phases (oils) are: liquid paraffins, silicone oils,natural vegetable oils such as sesame oil, almond oil, castor oil,synthetic triglycerides such as caprylic/capric biglyceride,triglyceride mixture with vegetable fatty acids of the chain lengthC₈-C₁₂ or other specially selected natural fatty acids, partialglyceride mixtures of saturated or unsaturated fatty acids possibly alsocontaining hydroxyl groups, mono- and diglycerides of the C₈-C₁₀ fattyacids, fatty acid esters such as ethyl stearate, di-n-butyryl adipate,hexyl laurate, dipropylene glycol perlargonate, esters of a branchedfatty acid of medium chain length with saturated fatty alcohols of chainlength C₁₆-C₁₈, isopropyl myristate, isopropyl palmitate,caprylic/capric acid esters of saturated fatty alcohols of chain lengthC₁₂-C₁₈, isopropyl stearate, oleyl oleate, decyl oleate, ethyl oleate,ethyl lactate, waxy fatty acid esters such as synthetic duck coccygealgland fat, dibutyl phthalate, diisopropyl adipate, and ester mixturesrelated to the latter, fatty alcohols such as isotridecyl alcohol,2-octyldodecanol, cetylstearyl alcohol, oleyl alcohol, and fatty acidssuch as oleic acid and mixtures thereof

Suitable hydrophilic phases are: water, alcohols such as propyleneglycol, glycerol, sorbitol and mixtures thereof

Suitable emulsifiers are:

non-ionic surfactants, e.g. polyethoxylated castor oil, polyethoxylatedsorbitan monooleate, sorbitan monostearate, glycerol monostearate,polyoxyethyl stearate, alkylphenol polyglycol ether;ampholytic surfactants such as di-sodium N-lauryl-p-iminodipropionate orlecithin; anionic surfactants, such as sodium lauryl sulfate, fattyalcohol ether sulfates, mono/dialkyl polyglycol ether orthophosphoricacid ester monoethanolamine salt; cation-active surfactants, such ascetyltrimethylammonium chloride.

Suitable further auxiliaries are: substances which enhance the viscosityand stabilize the emulsion, such as carboxymethylcellulose,methylcellulose and other cellulose and starch derivatives,polyacrylates, alginates, gelatin, gum arabic, polyvinylpyrrolidone,polyvinyl alcohol, copolymers of methyl vinyl ether and maleicanhydride, polyethylene glycols, waxes, colloidal silicic acid ormixtures of the substances mentioned.

Suspensions can be administered orally or topically/dermally. They areprepared by suspending the active compound in a suspending agent, ifappropriate with addition of other auxiliaries such as wetting agents,colorants, bioabsorption-promoting substances, preservatives,antioxidants, light stabilizers.

Liquid suspending agents are all homogeneous solvents and solventmixtures.

Suitable wetting agents (dispersants) are the emulsifiers given above.

Other auxiliaries which may be mentioned are those given above.

Semi-solid preparations can be administered orally ortopically/dermally. They differ from the suspensions and emulsionsdescribed above only by their higher viscosity.

For the production of solid preparations, the active compound is mixedwith suitable excipients, if appropriate with addition of auxiliaries,and brought into the desired form.

Suitable excipients are all physiologically tolerable solid inertsubstances. Those used are inorganic and organic substances. Inorganicsubstances are, for example, sodium chloride, carbonates such as calciumcarbonate, hydrogencarbonates, aluminium oxides, titanium oxide, silicicacids, argillaceous earths, precipitated or colloidal silica, orphosphates. Organic substances are, for example, sugar, cellulose,foodstuffs and feeds such as milk powder, animal meal, grain meals andshreds, starches.

Suitable auxiliaries are preservatives, antioxidants, and/or colorantswhich have been mentioned above.

Other suitable auxiliaries are lubricants and glidants such as magnesiumstearate, stearic acid, talc, bentonites, disintegration-promotingsubstances such as starch or crosslinked polyvinylpyrrolidone, binderssuch as starch, gelatin or linear polyvinylpyrrolidone, and dry binderssuch as microcrystalline cellulose.

In general, “parasiticidally effective amount” means the amount ofactive ingredient needed to achieve an observable effect on growth,including the effects of necrosis, death, retardation, prevention, andremoval, destruction, or otherwise diminishing the occurrence andactivity of the target organism. The parasiticidally effective amountcan vary for the various compounds/compositions used in the invention. Aparasiticidally effective amount of the compositions will also varyaccording to the prevailing conditions such as desired parasiticidaleffect and duration, target species, mode of application, and the like.

The compositions which can be used in the invention can comprisegenerally from about 0.001 to 95 wt % of the active compounds of themixtures of the present invention.

Generally it is favorable to apply the active compounds of the mixturesof the present invention in total amounts of 0.5 mg/kg to 100 mg/kg perday, preferably 1 mg/kg to 50 mg/kg per day.

Ready-to-use preparations contain the active compounds of the mixturesof the present invention acting against parasites, preferablyectoparasites, in concentrations of 10 ppm to 80 per cent by weight,preferably from 0.1 to 65 per cent by weight, more preferably from 1 to50 per cent by weight, most preferably from 5 to 40 per cent by weight.

Preparations which are diluted before use contain the active compoundsof the mixtures of the present invention acting against ectoparasites inconcentrations of 0.5 to 90 per cent by weight, preferably of 1 to 50per cent by weight.

Furthermore, the preparations comprise the active compounds of themixtures of the present invention against endoparasites inconcentrations of 10 ppm to 2 per cent by weight, preferably of 0.05 to0.9 per cent by weight, very particularly preferably of 0.005 to 0.25per cent by weight.

In a preferred embodiment of the present invention, the compositionscomprising the mixtures of the present invention are applieddermally/topically.

In a further preferred embodiment, the topical application is conductedin the form of compound-containing shaped articles such as collars,medallions, ear tags, bands for fixing at body parts, and adhesivestrips and foils.

Generally it is favorable to apply solid formulations which release theactive compounds of the mixtures of the present invention in totalamounts of 10 mg/kg to 300 mg/kg, preferably 20 mg/kg to 200 mg/kg, mostpreferably 25 mg/kg to 160 mg/kg body weight of the treated animal inthe course of three weeks.

For the preparation of the shaped articles, thermoplastic and flexibleplastics as well as elastomers and thermoplastic elastomers are used.Suitable plastics and elastomers are polyvinyl resins, polyurethane,polyacrylate, epoxy resins, cellulose, cellulose derivatives, polyamidesand polyester which are sufficiently compatible with the compounds offormula I. A detailed list of plastics and elastomers as well aspreparation procedures for the shaped articles is given e.g. in WO03/086075.

EXAMPLES

Some of the preferred compound I examples are characterized by theirphysical data in the following table C.I.2. The characterization can bedone by coupled High Performance Liquid Chromatography/mass spectrometry(HPLC/MS), by NMR or by their melting points.

The compounds were characterized by ¹H-NMR. The signals arecharacterized by chemical shift (ppm) vs. tetramethylsilane, by theirmultiplicity and by their integral (relative number of hydrogen atomsgiven). The following abbreviations are used to characterize themultiplicity of the signals: M=multiplett, q=quartett, t=triplett,d=doublet and s=singulett.

The compounds were also characterized by HPLC/MS. Analytical HPLCcolumn: RP-18 column Chromolith Speed ROD from Merck KgaA, Germany).Elution: acetonitrile +0.1% trifluoroacetic acid (TFA)/water +0.1%trifluoroacetic acid (TFA) in a ratio of from 5:95 to 95:5 in 5 minutesat 40° C.

Physical data of some specific compound examples of isoxazolinecompounds of formula I:

TABLE C.I.2 HPLC-MS ¹H NMR Compound (t_(r) = reten- (in CDCl₃): exampleStructure of compound I tion time) δ [ppm] C.I.73

t_(r) = 3.32 min; m = 494.0 ¹H-NMR (500 MHz,CDCl₃): = 8.50 (d, 1H), 7.95(m, 1H), 7.90 (m, 2H), 7.70 (m, 3H), 7.52 (s, 2H), 7.40 (m, 1H), 7.35(m, 1H), 7.25 (m, 1H), 4.75 (s, 2H), 4.10 (d, 1H), 3.75 (m, 1H). C.I.235

t_(r) = 3.40 min; m = 508.0 ¹H-NMR (500 MHz, CDCl₃): = 8.55 (m, 1H),7.70 (m, 1H), 7.50 (m, 5H), 7.45 (s, 1H), 7.40 (m, 1H), 7.25 (m, 2H),4.75 (d, 2H), 4.05 (d, 1H), 3.68 (d, 1H), 2.50 (s, 3H). C.I.240

t_(r) = 3.911 min; m = 556.1 ¹H-NMR (500 MHz, CDCl₃): = 7.42-7.58 (m,6H), 7.01 (br dd, 1H), 6.77 (br. dd, 1H), 4.20 (d, 2H), 4.08 (d, 1H),3.95 (m, 1H), 3.71 (d, 1H), 2.44 (s, 3H). C.I.397

t_(r) = 3.59 min; m = 544.1 ¹H-NMR (500 MHz, CDCl₃): = 8.85 (m, 1H),8.52 (m, 1H), 8.47 (m, 1H), 7.30-7.80 (m, 10H), 7.25 (m, 1H), 4.85 (m,2H), 4.26 (d, 1H), 3.88 (d, 1H).

Biology

Synergism can be described as an interaction where the combined effectof two or more compounds is greater than the sum of the individualeffects of each of the compounds. The presence of a synergistic effectin terms of percent control, between two mixing partners (X and Y) canbe calculated using the Colby equation (Colby, S. R., 1967, CalculatingSynergistic and Antagonistic Responses in Herbicide Combinations, Weeds,15, 20-22):

$E = \frac{XY}{100}$

When the observed combined control effect is greater than the expectedcombined control effect (E), then the combined effect is synergistic.

The following tests can demonstrate the control efficacy of compounds,mixtures or compositions of this invention on specific pests. However,the pest control protection afforded by the compounds, mixtures orcompositions is not limited to these species. In certain instances,combinations of a compound of this invention with other invertebratepest control compounds or agents are found to exhibit synergisticeffects against certain important invertebrate pests.

Test B.1 Control of Green Peach Aphid (Myzus persicae)

For evaluating control of green peach aphid (Myzus persicae) throughsystemic means the test unit consisted of 96-well-microtiter platescontaining liquid artificial diet under an artificial membrane.

The compounds or mixtures were formulated using a solution containing 75wt % water and 25 wt % DMSO. Different concentrations of formulatedcompounds or mixtures were pipetted into the aphid diet, using a custombuilt pipetter, at two replications. For experimental mixtures in thesetests identical volumes of both mixing partners at the desiredconcentrations respectively, were mixed together.

After application, 5-8 adult aphids were placed on the artificialmembrane inside the microtiter plate wells. The aphids were then allowedto suck on the treated aphid diet and incubated at 23±1° C., 50±5% RHfor 3 days. Aphid mortality and fecundity was then visually assessed.For the mixture tested the results are listed in table B.1.

TABLE B.1 Control of Green Peach Aphid (Myzus persicae)

Test compound is C.I.240: Green Peach Aphid ppm Average Control %Thiamethoxam + test compound C.I.240   0 + 2  0 0.4 + 0 25 0.4 + 2 100*Imidacloprid + test compound C.I.240     0 + 0.08  0 0.4 + 0  0   0.4 +0.08 100* *synergistic control effect according to Colby's equationTest B.2 Control of Boll Weevil (Anthonomus grandis)

For evaluating control of boll weevil (Anthonomus grandis) the test unitconsisted of 24-well-microtiter plates containing an insect diet and20-30 A. grandis eggs.

The compounds or mixtures were formulated using a solution containing 75wt % water and 25 wt % DMSO. Different concentrations of formulatedcompounds or mixtures were sprayed onto the insect diet at 20 μl, usinga custom built micro atomizer, at two replications.

For experimental mixtures in these tests identical volumes of bothmixing partners at the desired concentrations respectively, were mixedtogether.

After application, microtiter plates were incubated at 23±1° C., 50±5%RH for 5 days. Egg and larval mortality was then visually assessed. Forthe mixture tested the results are listed in table B.2.

TABLE B.2 Control of Boll Weevil (Anthonomus grandis)

Test compound is C.I.240: Boll Weevil ppm Average Control %Alpha-Cypermethrin + test compound C.I.240   0 + 0.4 50 0.08 + 0    00.08 + 0.4  100* Abamectin + test compound C.I.240   0 + 0.08  0 0.016 +0    50 0.016 + 0.08  100* Flonicamid + test compound C.I.240   0 + 0.450 4 + 0  0   4 + 0.4 100* *synergistic control effect according toColby's equation

In the following further test descriptions are given, which might alsobe used in order to evaluate the biological activity of the mixtures ofthe invention.

Test B.3

For evaluating control of vetch aphid (Megoura viciae) through contactor systemic means the test unit consists of 24-well-microtiter platescontaining broad bean leaf disks.

The compounds or mixtures are formulated using a solution containing 75wt % water and 25 wt % DMSO. Different concentrations of formulatedcompounds or mixtures are sprayed onto the leaf disks at 2.5 μl, using acustom built micro atomizer, at two replications.

For experimental mixtures in these tests identical volumes of bothmixing partners at the desired concentrations respectively, are mixedtogether.

After application, the leaf disks are air-dried and 5-8 adult aphids areplaced on the leaf disks inside the microtiter plate wells. The aphidsare then allowed to suck on the treated leaf disks and incubated at23±1° C., 50±5% RH (relative humidity) for 5 days. Aphid mortality andfecundity is then visually assessed.

Test B.4

For evaluating control of Mediterranean fruitfly (Ceratitis capitata)the test unit consists of 96-well-microtiter plates containing an insectdiet and 50-80 C. capitata eggs.

The compounds or mixtures are formulated using a solution containing 75wt % water and 25 wt % DMSO. Different concentrations of formulatedcompounds or mixtures are sprayed onto the insect diet at 5 μl, using acustom built micro atomizer, at two replications.

For experimental mixtures in these tests identical volumes of bothmixing partners at the desired concentrations respectively, are mixedtogether.

After application, microtiter plates are incubated at 28±1° C., 80±5% RHfor 5 days. Egg and larval mortality is visually assessed.

Test B.5

For evaluating control of tobacco budworm (Heliothis virescens) the testunit consists of 96-well-microtiter plates containing an insect diet and15-25 H. virescens eggs.

The compounds or mixtures are formulated using a solution containing 75wt % water and 25 wt % DMSO. Different concentrations of formulatedcompounds or mixtures are sprayed onto the insect diet at 10 μl, using acustom built micro atomizer, at two replications.

For experimental mixtures in these tests identical volumes of bothmixing partners at the desired concentrations respectively, are mixedtogether.

After application, microtiter plates are incubated at 28±1° C., 80±5% RHfor 5 days. Egg and larval mortality is visually assessed.

Test B.6

For evaluating control of bird cherry aphid (Rhopalosiphum padi) throughcontact or systemic means the test unit consists of 96-well-microtiterplates containing barley leaf disks.

The compounds or mixtures are formulated using a solution containing 75wt % water and 25 wt % DMSO. Different concentrations of formulatedcompounds or mixtures are sprayed onto the leaf disks at 2.5 μl, using acustom built micro atomizer, at two replications.

For experimental mixtures in these tests identical volumes of bothmixing partners at the desired concentrations respectively, are mixedtogether.

After application, the leaf disks are air-dried and 5-8 adult aphidsplaced on the leaf disks inside the microtiter plate wells. The aphidsare then allowed to suck on the treated leaf disks and incubated at25±1° C., 80±5% RH for 3 to 5 days. Aphid mortality and fecundity isvisually assessed.

1. A pesticidal mixture comprising 1) at least one isoxazoline compoundI of formula I:

wherein A is

and wherein # denotes the bond in formula I; R¹, R³ are independentlyfrom one another selected from the group consisting of hydrogen, chloroand CF₃; R² is hydrogen or chloro; R⁴ is hydrogen or CH₃, R⁵ ishydrogen, or R⁴ and R⁵ are together a bridging 1,3-butadienyl group,which form—together with the aromatic phenylring C they are attachedto—a naphtyl ring; or the tautomers, enantiomers, diastereomers or saltsthereof, and 2) at least one active compound II selected from A.4 anicotinic acteylcholine receptor agonist/antagonist selected from thegroup consisting of nicotin, cartap hydrochloride, thiocyclam and theclass of neonicotinoids consisting of acteamiprid, chlothianidin,dinotefuran, imidacloprid, nitenpyram, spinosad (allosteric agonist),spinetoram (allosteric agonist), thiacloprid, thiamethoxam and AKD-1022.2. The mixture according to claim 1, wherein the substituents of theactive compound I of formula I have the following meanings: A is A-1,A-4 or A-6; R¹, R³ are independently from one another selected from thegroup consisting of hydrogen, chloro and CF₃; R² is hydrogen or chloro;R⁴ is hydrogen or CH₃, R⁵ is hydrogen or R⁴ and R⁵ are together abridging 1,3-butadienyl group, which form—together with the aromaticphenylring C they are attached to—a naphtyl ring; or the tautomers,enantiomers, diastereomers or salts thereof.
 3. The mixture according toclaim 1, wherein the substituents of the active compound I of formula Ihave the following meanings: A is A-1, A-4 or A-6; R¹, R², R³ arechloro; R⁴ is hydrogen or CH₃, R⁵ is hydrogen or R⁴ and R⁵ are togethera bridging 1,3-butadienyl group, which form—together with the aromaticphenylring C they are attached to—a naphtyl ring; or the tautomers,enantiomers, diastereomers or salts thereof.
 4. The mixture according toclaim 1, wherein the substituents of the active compound I of formula Ihave the following meanings: A is A-1, A-4 or A-6; R¹, R³ are chloro; R²is hydrogen; R⁴ is hydrogen or CH₃, R⁵ is hydrogen or R⁴ and R⁵ aretogether a bridging 1,3-butadienyl group, which form—together with thearomatic phenylring C they are attached to—a naphtyl ring; or thetautomers, enantiomers, diastereomers or salts thereof.
 5. The mixtureaccording to claim 1, wherein the substituents of the active compound Iof formula I have the following meanings: A is A-1, A-4 or A-6; R¹, R³are CF₃; R² is hydrogen; R⁴ is hydrogen or CH₃, R⁵ is hydrogen or R⁴ andR⁵ are together a bridging 1,3-butadienyl group, which form—togetherwith the aromatic phenylring C they are attached to—a naphtyl ring; orthe tautomers, enantiomers, diastereomers or salts thereof.
 6. Themixture according to claim 1, wherein the substituents of the activecompound I of formula I have the following meanings: A is A-1, A-4 orA-6; R¹ is CF₃; R², R³ are hydrogen; R⁴ is hydrogen or CH₃, R⁵ ishydrogen or R⁴ and R⁵ are together a bridging 1,3-butadienyl group,which form—together with the aromatic phenylring C they are attachedto—a naphtyl ring; or the tautomers, enantiomers, diastereomers or saltsthereof.
 7. The mixture according to claim 1, wherein at least oneactive compound II is selected within group A.4 from thiocyclam,actamiprid, chlothianidin, dinotefuran, imidacloprid, nitenpyram,thiacloprid, thiamethoxam, AKD-1022 or spinosad.
 8. The mixtureaccording to claim 1, wherein at least one active compound II isclothianidin, imidacloprid or thiamethoxam.
 9. The mixture according toclaim 1, comprising the active compound I of the formula I and theactive compound II in a weight ratio of from 500:1 to 1:100.
 10. Amethod for protecting plants from attack or infestation by insects,acarids or nematodes comprising contacting the plant, or the soil orwater in which the plant is growing, with a mixture according to claim 1in pesticidally effective amounts.
 11. A method for controlling insects,arachnids or nematodes comprising contacting an insect, acarid ornematode or their food supply, habitat, breeding grounds or their locuswith a mixture according to claim 1 in pesticidally effective amounts.12. A method as claimed in claim 10 or 11, wherein the mixture accordingclaim 1 is applied in an amount of from 5 g/ha to 2000 g/ha.
 13. Amethod for protection of plant propagation material comprisingcontacting the plant propagation material with a mixture of claim 1 inpesticidally effective amounts.
 14. A method according to claim 13wherein the mixture is applied in an amount of from 0.1 g to 10 kg per100 kg of plant propagation material.
 15. A method as claimed in claim13, wherein the plant propagation material is/are seed(s).
 16. A seedtreated with the mixture according to claim 1 in an amount of from 0.1 gto 10 kg per 100 kg of seeds.
 17. A method for protecting animalsagainst infestation or infection by parasites which comprisesadministering to the animals a parasitically effective amount of amixture according to claim 1 to the animal in need thereof.
 18. A methodfor treating animals infested or infected by parasites which comprisesadministering to the animals a parasitically effective amount of amixture according claim 1 to the animal in need thereof.
 19. A method asclaimed in claim 10 wherein the active compounds I of formula I and theactive compounds II are applied simultaneously, that is jointly orseparately, or in succession.
 20. A pesticidal or parasiticidalcomposition, comprising a liquid or solid carrier and a mixtureaccording to claim 1.